SK175797A3 - Herbicidal ketals and spirocycles - Google Patents

Abstract

Compounds of Formula (I), and their agriculturally suitable salts, are disclosed which are useful for controlling undesired vegetation wherein Q is (Q-1) or (Q-2); R<1> and R<2> are each independently C1-C6 alkoxy, C2-C6 haloalkoxy, C1-C6 alkylthio or C2-C6 haloalkylthio; or R<1> and R<2> are taken together to form -X<1>-(CH2)r-X<2>-, -(CH2)s-X<3>-, -(CH2)t-X<3>-CH2-, -(CH2)v-X<3>-CH2CH2- or -(CH2)w-, each group optionally substituted with at least one member selected from 1-6 halogen, 1-6 CH3 and one C1-C3 alkoxy; or R<1> and R<2> are taken together to form -O-N(C1-C3 alkyl)-CHR<12>-CH2- or -O-N=CHR<12>-CH2-, each group optionally substituted with at least one member selected from 1-2 halogen and 1-2 CH3; or R<1> and R<2> are taken together with the carbon to which they are attached to form C(=O) or C(=S); and R<3>-R<10>, X<1>-X<3>, X, Y, Z, k, m, p, q, r, s, t, v, w, and x are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula (I) and a method for controlling undesired vegetation which involves contacting the vegetation or its environment with an effective amount of a compound of Formula (I).

Description

The invention relates to certain ketals and spirocycles, their agriculturally acceptable salts and compounds, and methods of using them in controlling undesirable vegetation.

BACKGROUND OF THE INVENTION

Control of undesirable vegetation It is very important to achieve high harvest. Achieving selective control of weed growth, in particular for crops such as rice, soy, sugar cane, corn, potatoes, wheat, barley, tomato and seed forest crops is highly desirable. Uncontrolled weed growth in these crops can cause a significant reduction in productivity, which entails an increase in consumer prices. Controlling undesirable vegetation on non-machined areas is also important. Many products are already on the market for these purposes, but there remains a need to find new compounds that are more efficient, cheaper, less toxic, more environmentally friendly or have different effects.

EP 283,261 discloses heterocycles of the general formula i as herbicides:

In which

X, X ¹ and ^R X are independently O or S;

R ¹ represents an inonocyclic or fused bicyclic hetero2 cyclic group optionally substituted by one or more of oxo, mercapto, balo, nitro, cyano, amino, monoalkylamino, dialkylamino, alkyl, amido, , cycloalkyl, haloalkyl, haloalkoxy, aryl, hydroxy, alkoxy, alkoxycarbonyl, mono or dialkylcarbamoyl, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylsulfonyl, alkylsulfonyl, sulfonamido; and

Y stands for inter alla, carbon.

an alkylene group of up to 4 atoms

The ketals and spirocycles of the invention are not part of this document.

SUMMARY OF THE INVENTION

The invention relates to compounds with all their geometrically agriculturally acceptable salts containing the following undesirable vegetation compounds:

of formula I, including: isomers and stereoisomers, agricultural compositions for use in control

in which □ stands for

are independently C 1 -C 1 alkoxy, C 2 -C 1 haloalkoxy, C 1 -C 6 alkylthio or C 2 -C ¹ haloalkylthio, or R ¹ and R ² together form -X ¹ - CH 2 ·; ) r-X '-, - C EIH-H. ^ - X ³ - »C CH.) tX ^ -CHs.-, -CCH-.) VX ³ -CHSCH _r - or -CCl-on ·) wherein each group may be optionally substituted with at least one member selected from the group consisting of 1 to 6 halogen atoms, 1 to 6 methyl groups, and one alkoxy group with 1 to 3 carbon atoms; or together R ¹ and R ^{2 may} together represent -O-NC (C 1 -C 3 alkyl) -CHR 11 ^and -CH 2 - or -O-N = CHR ^{1: 2} -CH ² -, wherein each group may be optionally substituted with at least one member selected from 1 to 2 halogen atoms and 1 to 2 methyl groups; or R ^{@ 1} and R ^@ 2 ^and together with the carbon atom to which they are attached may form C (--O) or CC = S);

X ¹ and X 1 are independently NC (C 1 -C 4 alkyl);

oxygen atom sulfur atom or

X ³ represents an oxygen or sulfur atom;

each R ³ is independently hydrogen or methyl;

R '* and R' ³ are independently 6 carbon atoms, carbon atoms, or 1 to 1 alkoxyalkylthio of 1 to E1; (C 1 -C 6), C (C 1 -C 6), H, (C 1 -C 6) alkyl, (C 1 -C 6) alkoxy, (C 1 -C 6), (C 1 -C 6), haloalkylthio (C 1 -C 6) , an alkylsulfinyl group a haloalkylsulfinyl group an alkylsulfonyl group of 1 to 2

Ei carbon atoms, halo-alkylsulfonyl having 1 to 6 carbon atoms, cyano, halogen or nitro;

R ⁶ is OR ¹ ', an alkylthio group having 1 alkylsulphinyl having 1 alkylsulphinyl having 1 sulphonyl having 1 to 6 sulphonyl having 1 to 6 carbon atoms, up to 6 carbon atoms.

up to E1 carbon atoms, halogenation of 6 carbon atoms, alkylatoms of carbon, haloalkylatoms of carbon, cyano, pinocyanate, thiocyanate, or halogen;

each R ² is independently C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio. 3 carbon atoms or halogen; or where two R ^* bound to the same carbon atom, then the pair of substituents R may together form a -OCH CH, _{and R} e) -, -OCH ^ CHaCHsO-, _and -SCH Cfk.S- or -SCHsäCHssCHjaS- and each it may be optionally substituted with one to four methyl groups;

R vod is hydrogen, C až-C alky alkyl, C až-C hal haloalkyl, C až-Ci alkoxyalkyl, formyl, C až-C alkyl alkylcarbonyl; C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl. E> carbon atoms, C 3 -C 7 dialkylaminocarbonyl, C 1 -C 6 alkylsulfonyl or halogen C 1 -C 6 alkylsulfonyl or R ^<5 'represents a benzoyl or phenylsulfonyl group which may optionally be substituted with C 1 -C 3 alkyl, halogen, cyano or nitro;

R ( ¹⁾ is hydrogen, (C1-C6) -alkyl, (C1-C6) -haloalkyl, (C3-C6) alkenyl or (C3-C6) alkynyl; or R ^ represents a phenyl or benzyl group which may be optionally substituted by an alkyl group having 1 to 3 carbon atoms, a halogen atom, a cyano group or a nitro group;

represents a hydrogen atom, an alkyl group of up to 6 atoms flashing, h and 1 to 6 carbon atoms, a halogen atom, a cyano group or a nitro group:

3-6 atoms.

R ¹¹ is H, alkyl, alkoxy, haloalkyl a'lkoxyalkylovú having 2 to 6 carbon atoms, a formyl group, an alkylcarbonyl group having 2 to 6 carbon atoms, alkoxycarbonyl of 2 to alkylaminocarbonyl group having 2 to dialkylaminocarbonyl having 3 to or ( ¹¹⁾ is benzoyl or phenylsulfonyl, which may optionally be substituted with (C 1 -C 3) alkyl, halogen, cyano or nitro;

having 1 to 6 carbon atoms, carbon atoms,

E carbon atoms, carbon atoms, up to 6 carbon atoms or 1 to 6 carbon atoms;

represents an alkyl group with .1. up to 3 carbon atoms; or ^R1S! represents a phenyl group which may be optionally substituted by a C 3 -C 3 alkyl group, a halogen atom, a cyano group or a nitro group;

means S (C) _r , O or NR ^:

R ¹³ represents a hydrogen atom, an alkyl carbon group, an alkenyl group having a C 3 -C 4 alkynyl group, C 3 -C 4 atoms, a carbon atom, a carbon atom, a formyl group, a C 2 -C 3 alkylcarbonyl group, a C 2 alkoxycarbonyl group up to 3 carbon atoms or an alkylsulfonyl group having from 3 to 2 carbon atoms;

Y represents an oxygen atom; a sulfur atom; NH; N (C -C alkyl); or CH ₅ optionally substituted with R 11 if q is not 0;

Z is a direct bond; an oxygen atom; SCO) α-; NH; NC (C ₁ -C ₃ alkyl); or CH-, optionally substituted with R ^x if q is not 0; provided that when Y is O, S, NH or N _{(C i.} ~ C ₃ alkyl), Z is a direct bond or CH. optionally substituted optionally with R ⁷ ;

where k is independently 0, 1 or 2, provided that the sum of k and m is 0, 1, or 2;

n and p are independently 0, 1 or 2;

q is 0, 1, 2, 3 or 4;

r is 2, 3 or 4;

s is 2, 3, 4 or 5;

t is 1, 2, 3 or 4;

v is 2 or 3;

u is 2, 3, 4, 5 or b;

x is 1 or 2; and z is 0, 1 or 2;

provided that (i) when X is S (O) _{r 1} , O is 0-1 and R ¹ and R ¹ are independently C 1 -C 6 alkoxy,

Ί C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio or C 2 -C 6 haloalkylthio, or taken together with the carbon atom to which they are attached (CC = O), then n is 1 or 2; and

(III) when X is an oxygen atom independently of ¹ and 1 or a alkoxy group of NR 1 to R ¹ and R ^{1 ;} are 6 carbon atoms, h 1 and γ per 1 alkoxy alkylthio group having 1 to (j alkylthio group having 2 to 6 carbon atoms, to which O is C'J-2).

up to 6 carbon atoms, carbon atoms or halogenated carbon atoms or together are taken together to form a CC == O), then

In the above definition, the term alkyl, whether used alone or in the wording of a compound such as a thioalkyl group or a haloalkyl group, includes a straight or branched chain alkyl group such as methyl, ethyl, n-propyl, i a propyl group or various butyl, pentyl or hexyl isomers. The term 1 to 6 methyl groups indicates that there are one to one of the available methyl substituent positions; the terms 1 to 4 methyl groups and 1 to 2 methyl groups are defined analogously. The term alkenyl includes straight or branched chain alkenes, for example

- P r o p e n y 1 o u s p u n u,

- propylene y and hexenyl isomers. polylyenes, for example 1, a branched alkynyl group, a, and various butenyl, pentenyl Alkenyl groups also include 2-propadienyl and 2,4-hexadienyl. The term includes straight-chain alkynyls or, for example, a 1-propiryl group, various butynyl, p-butynyl and hexinyl isomers. An alkynyl group includes groups consisting of a plurality of triple bonds, a 2,5-hexadiinyl group. Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy, and the various butoxy, pentoxy and hexyloxy isomers. The term alkoxyalkyl refers to

Η alkoxy-substitution at the alkyl group. Examples of alkoxyalkyl include, CHsOCHs ', CH _{3 ::} C) CI-L.CH _S., ΟΗ ΟΗ ^ ^ ΟΟΗ-., (I' C ₃ H _:: H> CH _and CH 2 OC H ₂ CH ₃ and CH 2 · OC H _with CH 3 The term "alkyl" includes straight and branched chain alkylthio groups, for example, methylthio, ethylthio and various propylthio, butylthio, pentylthio and hexylthioisomers. The term alkylsulfinyl includes both enantiomers and alkyl. Examples of the alkylsulfinyl group "include CH ₃ SCO),

CH35CH2.SC (O), CH3CH2CH3CH3 (SCO), CH _; . ₃ ) _{; and} CHSC (O) and various butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of alkylsulfonyl include, _{CH 3} SC O) 2, »CH35CH2.SC O) 2, CHgCHsCI-USCO) ^ CCH _{3) to the} CSC) _A, and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. The terms alkylamino and dialkylamino and the like. are defined anologically as above

C onscribedexamples.

The term halogen atom, either alone or in the verbal definition of compounds such as haloalkyl, includes a fluorine, chlorine, bromine or iodine atom. The term 1 to 6 halogen atoms indicates that there are one to honor substituted positions that can be substituted with independently selected halogen atoms. The term 1 to 2 halogen atoms is defined analogously. In addition, when used in a compound such as a haloalkyl group, the alkyl group may be partially or fully substituted by halogen atoms, which may be the same or different. Examples of haloalkyl groups include F ₃ C, C 1 CH ₂ , CF ₃ CH ₂ · and CF ₃ CCl 2.

The terms ha 1 og é to 1 alkoxy groups 1 og é na 1 ky 11 iogroups and the like, defined as allogical as the term haloogenoxy. Examples of haloalkoxy include CF 35 O, CCl? Cl? O, HCF ₂ O _and Salsa and CF ₃ CH _S .O. Examples of haloalkylthio groups include

CCI3S, cf ₃ s, sufiny 1 c h and CF3CF2.SCO).

C 1 C 3 R CHS and C1C H _of CH _and CH 2; S - EXAMPLE 1 h og Step alkyl groups include CC1 ₃ SCO), CF ^ SCO), CF3iCH2_.SC H) Examples ha1ogéna1k y1su1fony1ových en UPIN "include CCl ₃ SCO) _and. CF ₃ S (O) _second CF ₃ CH ₂ S (O) ₂ and CF ₃ CF _and SCO) _a . The prefix C C-Cj for some compounds denotes the total number of carbon atoms in the substituted group, with iaj being a number from 7 to 7. For example, a C 1 -C 6 alkylsulfonyl group denotes a methylsulfonyl to propylsulfonyl group. A C ₂ alkoxyalkyl group denotes CH 2 OCH 3, a C ₃ alkoxyalkyl group denotes, for example, CH 2 CHC (CH 2 O), CH 3 OCH 2 CH 3 or CH ₅ CH _and OCH 3; and CL ,. alkoxyalkyl designates the various isomers of an alkyl group having substitution of an alkoxy group containing a total of four carbon atoms, e.g. ΟΗ ^ ΟΗ ^ ΟΗ ^ ΟΟΗίϊ and CH ₃ CH _and OCH _and CH »- An example of an alkylcarbonyl group, for example, CCO) _CH3, CC O) CH _and CH _and CH ₃ and CC 0 CHCCH ₃ ) _s . Examples of the alkoxycarbonyl group are, for example, CH ₃ OCC = O), CH ₃ CH _and OCC = O), CH ₃ CH _and CH ₂ OCC = O), CCH _{3 S (} CHOCC-O) and various butoxy- and 1-ebopentoxycarbones. iz om é r y.

index then

If the compound is substituted with a lower substituent, which indicates that the number of substituents is greater than one, said substituents (if they exceed one) are selected. z o s p u n y d e f ”1 n o o o o e h s u b s t t e e t t.

If the group contains a substituent which may be a hydrogen atom, for example R ¹¹ or R ¹¹ , then when the substituent is taken as a hydrogen atom, it will be -; equivalent to a group that is unsubstituted.

considered

The compounds of the invention may exist as one or more of these. z om é r o v. d i a s t e r e om e r y,

Various stereoisomers include enantiomers, atropisomers and geometric isomers. Is a-; it will be appreciated that one of the stereoisomers may be more potent and / or may exhibit the desired effects when present at a higher concentration than the other stereoisomers, or if it is separated from the other stereoisomers. In addition, one skilled in the art knows how to separate, enrich and / or selectively prepare said stereoisomers. As mentioned above, the invention encompasses compounds selected from compounds of Formula I and agriculturally acceptable salts thereof. The compounds of the invention may exist as mixtures, stereoisomers, as stereoisomers, or as an optically active form.

each

Certain compounds of the invention may exist as one or more tautomers. For example, it will be appreciated that compounds of formula Ia (formula Ie in which Q is Q-1) in which R * ⁵ * is OR ¹¹ and R ¹¹ is hydrogen may exist as both tautomers, as will be shown below . It will be appreciated by those skilled in the art that these tautomers often exist in equilibrium with each other. Since these tautomers convert under normal ambient conditions, they provide the same biological effects. The invention includes mixtures of these tautomers as well as individual tautomers of the compounds of formula I.

ia

Salts of the compounds of the invention include salts of inorganic or organic acids, for example, hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, melonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic acid. These salts of the compounds of the invention also include those obtained when the compound contains an acid group, for example an enol group, by reaction with an organic base Cnapr. pyridine, ammonia or triethylamine) or with inorganic bases (Cnapr. hybrids, hydroxides or carbonate of sodium, potassium, lithium, magnesium or

t) and naked).

Preferred compounds for better efficiency and / or easier synthesis are:

Preferred first compounds of formula I as defined above and agriculturally acceptable salts thereof, in which:

each R ⁷ is independently an alkyl group containing 1 or 6 carbon atoms;

-C 3 marks AM en s SGJ) _r;

Y and Z are independently C1-1. optionally substituted with R 6;

k is 0; and is 1.

Preferred second of which:

Compounds are preferred first compounds

and ^{r and} R are independently C 1 to 6 carbon atoms, haloalkoxy of 2 to 6 carbon atoms, alkylthio of 1 to b carbon atoms, or halogenoalkylthio having 2 to b carbon atoms; or R ¹ and R ¹ together form -X ¹ -G ¹ : i _a ) _Γ- Χ 1 "optionally substituted by at least one member selected from 1 to E; halogens and 1 to 6 methyl groups; or R ¹ and R ^a together represent the carbon atom to which they are attached, C (= O);

X ¹ and X ^{: and} are both oxygen or sulfur;

m is 1 or 2; and

1.2 means 2 or 3.

Preferred third compounds are preferred second compounds in which:

R ⁴ and R ^s are independently hydrogen, alkyl of 1 to 3 carbon atoms or a hydrogen atom;

R ⁵ represents an alkyl group having 1 to 3 carbon atoms;

R ^<;> is H, alkyl of 1 to 6 carbon.

C 3 -C 6 alkenyl;

represents a hydrogen atom;

R ¹¹ is hydrogen, -CHO, alkylkarboriylovú having two to ten carbon atoms, alkoxycarbonyl or aroyl having from 2 to 6 carbon. C 2 -C 6 alkylaminocarbonyl, C 3 -C 7 dialkylaminocarbonyl, C 1 -C 6 alkylsulfonyl or C 1 -C 6 haloalkylsulfonyl; or R ¹¹ is benzoyl or phenylsulfonyl, which may be optionally substituted by C 1 -C 3 alkyl, halogen, cyano or nitro; and is 2

Preferred fourth compounds are preferred third compounds in which:

R ^x and R ³² are methoxy; or R ¹ and R ^a together form a CH-X-C _and ¹⁾ R ³² -; or R ¹ and R " ^! form together with the carbon atom to which they are attached (CC = O);

X ¹ and X ^: '' represents an oxygen atom;

R ^k and R ^s are independently hydrogen, methyl, and thiophene;

R ^a is OR ^11;

rb represents a hydrogen atom or an alkylsulfonyl group having 1 to 6 carbon atoms; or R ^a represents a benzoyl or phenylsulfonyl group, each of which may be optionally substituted with a C 1 -C 3 alkyl group, a halogen atom, a cyano group or a nitro group;

R ¹¹ represents a hydrogen atom or an alkylsulfonyl group having 1 to 2 carbon atoms; or R ¹¹ is benzoyl or phenylsulfonyl, each of which may be optionally substituted with C 1 -C 3 alkyl, halogen, cyano or nitro;

m is 1; and r is 2.

Preferred fifth compounds are preferred fourth compounds wherein:

^R is methyl or halogen and is attached to the phenyl ring position adjacent to the SCOT) r - group.

Preferred sixth compounds are preferred fifth compounds wherein:

O is 0-1.

Preferred seven compounds are preferred six compounds wherein:

□ stands for O-2.

Most preferred compounds are preferred second compounds selected from the group consisting of:

2-C (2,3-dihydrospl.roE 4/7-1-benzothiopyran-4,2'-C1,33'-oxolan-3-yl) carbonyl-1,3-cyclohexanedione, S'-dioxide ·,

C 2,3-dihydrospiro (4W-1-benzothiopyran-4,2'-1,3,3-dioxolan-3-yl) (1-ethyl-5-hydroxy-1H-pyrazol-4-yl) nietanone S, S'-dioxide;

2-1 (2,3-dihydro-5,8-dimethylspiroC 4,7-l-benzothiopyrari-4,2'-1,3,3-dioxolol-6-yl) -1-arbonyl-1,3,3-cyclohexanedione S, S-dioxide ;

(2,3-Dihydro-5,8-dimethylspiro E4 / 7-1-benzothiopyran-4,2'-E1,33-dioxolin-3-6-yl) C1-ethyl-5-hydroxy-1 -7-pyrazole 4-yl) ethanone 5 ', S'-d 1 oxide;

6-EC 1-ethyl-5-hydroxy-1H-pyrazol-4-yl) carbonyl-2,3-dihydro-5,8-dimethyl-4- (7-1-benzothiopyran-4-one) -1, 1.-d .1 oxide;

2-1 (2,3-dihydro-5,8-dimethylspiro [4,7-1-benzothiopyran-4,2'-1,3,3-dioxolanl-6-yl) carbonyl] -1,3-cyclohexanedione;

C 2, 3 - dihydro-5,8-dimethyletro spiro C 4 / 7-1 - benzo: L opyrate - 4, 2 '- L 1, 3 3 d 1 cxo lan3 -6-yl (1-ethyl-5-hydroxy-1 H -pyrazol-4-yl) methanone.

The invention also relates to herbicidal compositions comprising herbicidally effective amounts of the compounds of the invention and at least one surfactant, solid diluent or liquid diluent. Preferred compositions of the invention are those containing the preferred compounds described above.

The invention relates to a method for controlling undesirable vegetation, comprising: administering a herbicidally effective amount of the compounds of the invention Cnapr. in the form of a composition described herein) to the locus of vegetation. Preferred uses are those that include the above preferred compounds.

Compounds of Formula I may be prepared by one or more of the following methods and variants thereof, including Reaction Schemes 1 to 22. Definitions of Q, R ¹ to R ¹³ , X ¹ to X ³ , X, Z, k, m, n, p, q, r, s, t, v, w, x and z in the compounds of formulas I to XVIII are as defined in the Summary of the Invention. Compounds of formulas Ia to Ic are subsets of compounds of formula I and all substituents in compounds Ia to Ic have the same meaning as for compounds of formula I in which O is 0-1.

ia

Reaction Scheme I illustrates the preparation of compounds of formulas Ia and CR ¹ and R 2 ^, together with the atom to which they are attached, form O (== 0) and CC = S), R ⁶ is OR ¹⁴ and R ¹¹ is as defined above. According to the present invention, it is not a hydrogen atom, said method comprising providing a compound of formula (Ia) (R ¹ and R ² do not form together with the carbon to which they are attached, C (= O) and C (= S), R " ⁵ * means OH) to react with a reagent of formula II in the presence of a base wherein X 1 is chloro, bromo, fluoro, trifluoromethanesulfonate or acetate and R ¹ is as defined above. The coupling is carried out in a manner well known in the art, see, for example, K. Nakamura et al., WO 95/04054.

Reaction scheme 1

The (R ¹ and R ^R 'do not form together with the carbon to which the N a + X * R ** attached form C (= 0) and 6 (== 5), ^R6 is OH) CR ¹ Ia and R ^Do not form> together with carbon, on

The base that is bound,

600) and C (= S), R ^Ä means OR ¹ *)

Reaction Scheme 2 illustrates the preparation of compounds of formula Ia (R 'a

R ^{2 is} not taken together to form the carbon to which the carbon compound is bound, 600) and 6 (== 6), R ⁶ is S (O) _y R ¹⁵ ; y is 1 or 2; ^and R ^LS5 is alkyl of 1 to 6 carbon atoms or haloalkyl having 1 to 6 carbon atoms), in which the »formula Ia (R ¹ and R do not form with ^R to which they are attached, 6 (== 0 ) and 6 (= 5), R * ⁵ * means

5R ( ^1S ) is reacted with an oxidizing agent, for example, peracetic acid, other peroxybenzoic acid, peroxymonium sulphate or hydrogen peroxide (the reaction may be buffered with a base such as sodium acetate or sodium carbonate). The oxidation is carried out by methods well known in the art, see for example B. 1 * 1. Trost et al., J. Org. Chem. (1988) 53,532; B. 1 * 1. Trost et al., Tetrahedron Let t. (1,981), 21, 1287; and 5. Patai et al., The Chemietry of Sulphone and Sulphoxideo, John Wiley & Sons.

Scheme 2 Ia (R ¹ and R ⁵² do not form together> with the carbon to which they are attached to, C (= 0) and 6 (= 5), R ^A represents S (O) ^ R ^{1 S,} y is 1 or 2) Ia (R ^{1 and} R do not form ^{together, and} oxidizing the carbon to which they are attached, 6 (= 0) and 6 (= 5), R ^f is an agent SR ¹⁵³⁾

The compounds of formula Ia (R ¹ and R ^f do not form together with the carbon to which they are attached, 6 (= 0) and 6 (= S) R ⁵ * is S (O) _x R ^{1 S,} y is 1, or 2, and R ^{1 s} is as defined above and R ¹⁰ represents a C1 haloalkyl group of 1 to E> alkoxyalkyl group of experts on to E!

carbon atoms or 2 to ES carbon atoms) is possible in the art from a compound having general carbon atoms of formula Ia (R ³

R = do not form together with the carbon to which they are attached (CC = (O) and CC-S), R ^{: L (1)} represents a halogen atom) by treatment with a nucleophilic reagent of formula III CHSR ' ^S , HCN, HSCN, HOCN or HOR ¹ * '; h represents Na, Cu, K or Li), as shown in Reaction Scheme 3, using general methods well documented in the literature C see, for example, S. Hyiano et al., J. C'hem. Soc., Perkin Trans. 1 (1976), 1146; PH Nelson and JT Nelson, Synthesis ® 1992), 12, 1287-1291; S. luller et al., DE 4241999-A1).

Reaction Scheme 3 with the carbon to which they are attached (CC = O) and CC = S) represents a halogen atom)

pole HSR ¹⁵ la CR ¹ and R on the- + or > with carbon, , R ^Ä HOR ¹ * bound, C or means SR HCN or OR ¹ * ⁵ or HSCN or HOCN III

² do not form together on which they are (C = 0) and CC = S), R * ^1S CN, SCN, OCN

The compounds of formula Ia CR ¹ and R ² do not form with the carbon to which they are attached, CC = O) CC = S), R ^t> is a halogen) can be prepared by reacting a compound of formula Ia CR ^1, and R ² do not form together with the carbon to which they are attached (CC = O) and CC = S), R ¹⁵ * is OH) to react with a halogenating agent, for example oxalyl bromide or oxalyl chloride (C) 4). the conversion is carried out: in the art in general: by known methods, see for example S. Hüller et al., UO 94/13619;

Hüller et al., DE 4241999-A1.

R e: Actuation: H a 4 l CR ^X and R ² do not form together with the carbon to which they are attached (CC = O) and CC = S), R ⁶ represents OH)> ¹ and R 1 ² do not together form a halogenator with the carbon to which the naphthaic reagents are bound, CC = O) and CC = S), R ** 1 o / e.g. EMI4.0 [0040] EMI4.0 [0100] OR ⁽ 1) oxalyl bromide, oxalyl chloride

Reaction Scheme 5 illustrates the preparation of compounds of formula (Ia ⁾ and CR ¹ and R ² together with the carbon atom to which they are bonded (CC == □) are formed, wherein the compound of formula (Ia ⁾ is independently alkoxy; 1 to 6 carbon atoms or R ^{: L} and R ²² do not form - OCCH), - O-) is stirred in an aqueous solution of hydrochloric acid or hydrobromic acid (0.1N to 12M) at temperatures ranging in the temperature range from 0 ° C to 100 ° C for 00 minutes to 3 days. This conversion is accomplished by methods known in the art, see, for example, PA

Grieco a k o] ..... J. Not even. Chem. Soc. C1977), 99, p. 0773; P. A.

Grieco et al., J. Org. Chem. 78 1.978), 43, p. 4178th

Reaction Scheme and E) 1a are CR ¹ and R ^a are independently alkoxy having 1

HCl / H ₂ O (R ¹ and R 2) together form with a carbon atom to which up to 6 carbon atoms or or HBr / H _and O are bonded, CC-O) R ¹ and R ² together form -OC CH -,) _r 0-)

Reaction Scheme 6 illustrates the preparation of compounds of Formula Ia and CR ¹ and R '''form a carbon atom to which they are attached together (CC = O) and CC = S) and R **' is OH) in which the enol ester is of formula IVa ^{R: I,} and R ^L 'taken together with the carbon to which they are attached, CC = O) CC = s)), and / or its regioisomer of formula IVb, reacted: with a base, for example triethylamine in the presence of a catalytic amount of cyanide source C, e.g. acetone cyanohydrin and cyanide. potassium salt). This rearrangement is carried out by conventional methods known in the art: see, for example, WJ Michael, EP 0389803-A1; D. Carwright et al., EP 0283261-B1.

R e a tio n s 6

(R ¹ and R ^a do not form together with the carbon atom to which they are attached C (== 0) and C (= S))

Base C (e.g. triethylamine)

A cyanide amount or source in a catalytic e.g. potassium acetone cyanohydride) 1a (R ¹ and R ²¹ do not form together with the carbon atom to which they are attached, CC = O) and C (= S), R ⁶ represents OH)

The enol esters of formula IVa CR ¹ and R ²¹ do not form together: with the carbon atom to which they are attached, C (= O) and C (= S)) and / or their regioisomer of formula IVb can be prepared by introducing a dicarbonyl compound of formula V to react: with an acid chloride of formula VI, CR ¹ and R 2 ^and do not form together: with the carbon atom to which they are attached (C (= O) and CC = S)) in the presence of a slight molar excess of base is: for example triethylamine, in an inert organic solvent, for example acetonitrile, methylene chloride or toluene, at. temperatures ranging from 0 ° C to 110 ° 0 (Reaction Scheme 7). This type of coupling is carried out by conventional methods known in the art, see for example WJ Michael, EP 0369803-A1; D. Carwell, et al., EP 0283261-61.

Reaction scheme 7

(R ^A and R ² do not form together with the carbon atom to which they are attached C (= O) and C (= S) 5

Base (e.g. triethylamine)

IN

IVa and / or IVb

CR ¹ and R ^2, together with the carbon atom to which they are attached, do not form C (= O) and C (= S>)

Acid chlorides of formula VI (CR ¹ and R ^{2) do not form} together with the carbon atom to which they are attached (C (= O) and C (= S)) can be prepared by introducing an acid of formula (VII) CR ¹ and R ² together: with the carbon atom to which they are attached, C (= O) and C (= S)) to react: with oxalyl chloride (or thionyl chloride) and a catalytic amount of dimethylformamide (Reaction Scheme 8). This chlorination is well known in the art, see for example WJ Michael, EP 0369803-A1.

Reaction scheme 8

Oxalyl chloride (or thionyl chloride) vn

- _> (catalytic amount of N, N -dimethylformamide) (R ¹ and R ² do not form together with the carbon atom to which they are attached 0 (= 0) and C (= S))

VI (R ¹ and R ² do not form together with the carbon atom to which they are attached C (= O) and C (= S))

Reaction Scheme 9 illustrates the preparation of an acid of formula VII CR ^X and R ² do not form together: with the carbon atom to which they are attached (CC = O) and CC = S); X is SCO) _r, n is 1 or 2), whereby the acid of formula VII (R ¹ and R '''do not form together with the carbon to which they are attached, C ¢ = 0) and the CC-S) ; X is S) reacted with an oxidizing agent, such as peracetic acid, n-chloroperoxybenzoic acid, or hydrogen peroxide. The reaction can be put through with a base, for example sodium acetate or sodium carbonate. The oxidation is carried out by conventional methods known in the art

C see, for example, B. M. Trest et al., J. Or <3. Chem. C1988, 53, 532; B. 1 * 1. Trost et al., Tetrahedron Lett. C1981, 21, 1287; S. Patai et al., The Chemistry of Sulphones and Sulphoxides, John Wiley & Sons).

R e: a n d e s: h e a 9

VII

CR ¹ and R ^a do not form together with the carbon atom to which they are attached (CC = O) and CC = S); X - S)

Oxidizing>

agent

VII

CR ^1, and R ^a - i monster with the carbon atom to which they are attached, CC = O) CC = S);

X = SCO) _r = an = 1 or 2)

Reaction Scheme 10 illustrates: the preparation of acids of formula VII (R 1 and R 2) do ^{not form} together with: the carbon atom to which they are attached (CC = O) and CC-S); X represents a sulfur atom, an oxygen atom or NR ¹³ ) in which the phenyl bromide of the general formula VIII (CR ¹ and R ^{a) is} not formed together with the carbon atom to which they are attached (CC = O) and CC = S); X represents a sulfur atom, an oxygen atom or NR ¹³ ) treated with t-butyllithium (C) or magnesium) and 111 on the in situ salt is then reacted with carbon dioxide and then acidified with an acid such as hydrochloric acid. This conversion is carried out by conventional methods known in the art, see for example 1 * 1. A.. Ogliaruso et al. Synthesis oF Carboxylic Acids, Esters and Theis Derivates, p. 27-28, John Wiley &amp;Sons; AJ Bridges et al., J. Or <3. Chem. (C1990), 55 (C2), 773; C. Frank et al., Arr / eu. Chem. Int. Ed. Some instances of incorporation of deprotection and deprotection sequences or internal conversion of a functional group into synthesis will help to obtain the desired products, the protecting groups will be apparent to those skilled in the art (see, for example, Green TW: Wuts, P. Groups in Organic Synthesis, 2nd edition, Wiley

Use and Selection of Synthetic Syntheses G.ll., Protective

Neu York, 1991).

Reaction scheme 10

1) r-BuLi (or ilg)

2) COs.

>

3) H ^(+> (R ¹ and R ² do not form together with the carbon atom to which they are attached C (= O) and C (= S); X represents a sulfur atom, an oxygen atom or NR ¹³ )

VII (R ¹ and ^R do not form together with the carbon to which they are attached to form C (= O) and C (= S), X is S, O or MR ¹³⁾

Scheme 11 illustrates the preparation of phenyl bromide of Formula VIII (R ¹ and ^R are independently C 1 -C 6 alkyl, halogeno C 1 -C 6 alkyl, alkyltioskuplrtu of 1 to 6 carbon atoms or halogenoalkylthio having 1 to 6 carbon atoms; or R ¹ and R ² - "together form -X ^x - (CH ² >) (-.- X ¹ - ² - optionally substituted with at least one member selected from the group consisting of 1 to 8 halogen atoms, 1 to 8 methyl groups and one alkoxy group X ¹ and X ²¹ have the same meaning as described in the Summary of the Invention and X represents a sulfur, oxygen or NR ¹³ atom in which a ketone of formula IX (X represents a sulfur, oxygen or MR ¹³ ) reacts with an alcohol, an alkylthiol or HX ¹ - (CH 2) 2 - (R 1) (optionally substituted with at least one member selected from the group consisting of 1 to 8 halogen atoms, 1 to 8 methyl groups) n and one (C 1 -C 3) alkoxy group; X ¹ , X ¹² and ar are as defined in the Summary of the Invention, in the presence of a protic acid catalyst such as p-toluenesulfonic acid (or Lewis acid, e.g.

BF -, in an inert organic solvent such as toluene or alcohol (when the alcohol is a reagent). This conversion is carried out by conventional methods known in the art, see for example T. Ul. Greene et al. Protective Groups in Irganic Synthesis C second edition), p. 175-221, John Wiley &amp;

Reaction scheme

R ⁴

alcohol, alkylthio, or HX ^x - (CH ₂ ), -X ² H>

(catalytic acid) ⁽² R

VIII

R ²² is

X is S, O or ^NR13, independently: C _{x R-C} alkoxy, C -C alkoxy, halo, C -C alkylthio or C-C ^ haloalkylthio; or R ¹ and R ² together: form a -X ¹ - (CH _{S.) r.-X} ² - or; substituted with at least one member selected from the group consisting of: 8 halogen atoms, methyl groups one C 1 -C ₃ alkoxy; X ² and r are as defined in the Summary of the Invention and X is S, O or NR ¹³ ) of a

X ¹ Scheme 12 Formula VIII

The reaction of general each illustrate: f enylbromidov preparation of ⁽² R

R ² together are - (CH _R), that group may: be optionally: substituted with at least one member selected from the group Ei 1 to halogen atoms, 1-8 methyl groups, and one C 1 -C 3 alkyl; and X represents a sulfur atom, an oxygen atom or NR ¹³ ) according to which a ketone of the general formula IX (X represents a sulfur atom, an oxygen atom or NR ¹³ ) is reacted with a Grignard reagent, sulfoniumeylloalkylide, lithium lithioalkoxide, equivalent reagents in an inert organic solvent. Some of the intermediates may be further modified by reaction of Reaction Scheme 12 to provide the desired phenyl bromides of formula VIII. The above reactions are carried out using methods known in the art (or using some minor modifications to these methods), see e.g. S. Umio et al., J. Ded. Chem. 1972, 15, p. 855; B. Ludryk et al., J. Orq. Chem. C1989), 54 (24), p. 5657; Z. Paryzek et al., Can. J. Chem. ¢ 1987), 65 ¢ 1), p. 229; B. ľl. Trost et al.,

J. Am. Chem. Soc. 1972, 94, p. 4777; B. ΙΊ. Trost et al., J. Am. Chem. Soc. 1985, 107, p. 1778; S. Fukuzawa et al., J.

Chem. Comm. (1980, 8, p. 624; JF 611 et al., Tetrahedron (1994), 50 (11), p. 3437; TJ Jenkins et al.,. Org. Chem. ¢ 1.994), 59 (6) , p. 1485; Li, C.J. et al., Organometallics (1991), 10 (8), p. 2548; E.J. Corey et al., J. Am. Chem. Soc. ¢ 1965), 87, p. 1353; K. Okuma et al., J. Orq. Chem. 1983, 48, 5133.

Reaction scheme 12

Grlgnard's reagent, with 1-phenylamine and 1-yl 11 d, lithium lithium alkoxide, organopalladium reagent, sulfonium ylide or other equivalent reagent

IX __ ......>

(X stands for

C 'f

or NR ¹³ )

VIII (R ¹ and R ' ² together form -CCH ² ) s -O-, - (CH-) tX ³ -CHa-,

- (CH 2) 2 -X ³ -CH _with CH 2 - _; - or - (CH ₂ ) _W -, each group may be substituted by at least one member selected from 1-8 halogens, 1-8 CH ₃ and one C 1 -C 8 alkoxy; and X is S, O or NR ¹³ )

Reaction Scheme 13 illustrates the preparation of phenylbromides of formula VIII (R ¹ and R ^{22 taken} together are - (68 R) -8- optionally substituted by at least one member selected from the group consisting of 1 to 8 halogen atoms, one to eight methyl groups and one alkoxy group with 1 X is sulfur, oxygen or NR ³¹ ) in which a thioketone of formula X (X is sulfur, oxygen or NR ¹³ ) is reacted with a dibromoalkane of formula XI in the presence of an equimolar amount or a higher amount of Yb metal in an inert organic solvent, for example a mixture of benzene and hexamethylphosphoric triamide

This conversion is, for example, Y customary in the art known to those skilled in the art of laccoli et al., Chem. Lett. ¢ 1994), methods 511.

see

R e a k C h a c h e a c 13

X

Br - _{r 2} CCH) _with Br (optionally substituted by at least one member selected from 1-8 halogen, 1-8 _CH3 one C _x -C ₃ alkoxy)

(X, S, O or NR ¹³ )

> VIII (R ¹ and R ^and together: consists of - (CH--,), - S- eventually substi- at least one Ným member- Ným from 1-8 halogen- new Moon, 1-8 CH ₃ and one- it C _x -C ₃ alkoxy; and X is S, O aleb o NR ¹³ )

Some of the compounds of Formula VIII (k is 0, R ¹ and ^R together form a - (CH a) '-X ³ -, CH-C.) TX ³ -CHÄ-, -CCHs.) _In ³ -X -CH ₂ CH 3 - or -CCH 4 ( _R 1) -, each group may be optionally: substituted by at least one member selected from 1 to 8 halogen atoms, 1 to 8 methyl groups and one alkoxy group having 1 to 3 carbon atoms), may be prepared by reacting an unsaturated alkyltiofenylbromidu of formula XII is reacted with a Lewis acid such as SnCl ^ or AlCl ^, or an acid such as trifluoroacetic acid or polyphosphoric acid in an inert solvent such as, e.g., C H _and C _ffi, at a temperature of a temperature range of 0 ° C to 110 ° C for a time ranging from 30 minutes to 3 days (Reaction Scheme 14). This conversion is carried out by conventional methods known in the art, see for example 1 * 1. J. Dauson et al., J. Med. Chem. (1984), 27, (11), p. 1516; HG Viehe et al., J. Chem. Soc., Chem. Cammun. (1995), (10), p. 993rd

CX stands for S, O or NR ¹³ )

Reaction scheme 14

AlCl ₃ , SnCl 4, CF 3 CO 4 H or polyphosphoric acid

VIII

C k is O; and X is S, O or NR ¹³ ) (R ¹ and R ³² together form

-C (CH3) n- ³ -. - (CH 6) n -X ³ -CH 2 -.

CH-C.) _In CH ³ -X _{and the} CH - or

- (CH ₂ ) _U -, each group may be optionally substituted with at least one member selected from 1-8 halogens,

1-8 CH ₃ and one C 1 -C ₃ alkoxy)

Some compounds of formula VIII (k is 0; R ¹ and R ³² together form CH ³ ) SX ³ -, - (CH 2) 3 X 2 -CH 2 -, - (CH 2) _in -X 2 -CHaCH 2 - or - (CH ₂ ) _M -, wherein each group may be optionally substituted with 1 to 8 halogen atoms, 1 to 8 methyl groups and one alkoxy group with 1 to 3 carbon atoms), may be prepared by introducing a chloroalkylthiophenyl bromide of formula XIII (X is sulfur) , an oxygen atom or NR ¹³ ) with a compound of formula XIV in the presence of a Lewis acid such as SnCl 4, EtAlCl ₃ or AlCl ₃ in an inert organic solvent such as CH 2 Cl 2 at a temperature ranging from D ° C to 110 ^C, C at a time ranging from 15 minutes to 3 days (Reaction Scheme 15). This conversion is carried out in a manner known per se, see, for example, Y. Tamura et al., Tet. Lett. (1981) p. 3773; H. Ishibashi et al., J. Chem. S'oe. Chem. Commun (1988), (12), p. 827th

Reaction scheme 15

(X represents S, O or NR ¹³ ) XIII

Leuis acids (e.g. SnCl 2, EtAlCl ₃ or AlCl ₃ )

wherein j is 0, 1 or 2 VIII (k means 0 and X are WITH, 0 or NR ¹³ )

Reaction Scheme 16 illustrates the preparation of phenyl bromides of formula VIII (k is 0; R ¹ and R ² - together form

-CH _and CH _and -, optionally substituted with at least one member selected from the group consisting of 1 to 4 halogen atoms, 1 to 4 methyl groups, and one alkoxy group with 1 to 3 carbon atoms; or R ¹ and ^R together form a -O-C-NC _C3 alkyl) -CHR ^{1 S} ^ CH., wherein each group is optionally substituted with at least one member selected from the group consisting of 1 to 2 halogen, 1 to 2 methyl groups; and X is S, O or NR ^13), in which the alkene of Formula XV (X is S, /

an oxygen atom or NR ¹³ ) is reacted with a Wittig reagent, a lemon, a silyl nitronate, a nitriloxide or a Simmons-Smith reagent in an inert organic solvent. Some of the intermediates of Reaction Scheme 16 may be further modified to provide the desired phenyl bromides of Formula VIII. The above reactions are carried out by methods known in the art (or little modification thereof), see, for example, R. Flechoulam et al., J. Am. Chem. Soc. (1958), 90, p.

4386; And.

Hosomi et al., Chem

Lett. C1985), (7), p. 1049; WITH.

lzengeza et al., J. Chem. Soc. Chem. Commun. 1984, 9, p. 606; H. litsu et al., Tet. Lett. ¢ 1983), 24 CIO), p. 1049; J. E. Baldwin et al., J. Chem. Soc. Chem. Commun. C1968), p. 373; S.L. loffe et al., J. Gen. Chem. USSR (English translation) ¢ 1973),

43, p. 1699; A. Brandi et al. Tet. Lett. ¢ 1987) 28 (32), p. 3845; D. P. Curran et al., J. Org. Chem. (1984) 49 (20), p. 3474; R. J. Rauson et al., J. Org. Chem., (1970), 35 (5), p.

2057th

RL7

(X is S, O or NR ¹³⁾

R ¹⁷ and R ¹¹ are independently H, halogen or CH ₃

Reaction scheme 16

Wittig's reagent, nitrile, silylnitronate> ym nitriloxide or (k stands for 0; R ¹ and R ²

Simmons-Smith together form a reagent -CH 2 CH 2 -, - optionally substituted with at least one member selected from 1-4 halogens, 1-4 CH 3; and one C 1 -C ₃ alkoxy; or R ¹ and R ² together form a -N-f (Ci-3 alkyl) -CH-CHS ^12, wherein each group is optionally substituted by one member selected from 1-2 halogen, 1-2 CH _S; and X is S, O or NR ¹³

Some compounds of formula VIII (X is sulfur, oxygen or NR ¹³ ) can be prepared by reacting a substituted benzene of formula XVI (X is sulfur, oxygen or NR ¹³ ) with bromine in an inert organic solvent (reaction 17). This bromination is carried out by methods known in the art, see, for example, E. Campaigne et al., J. Heterocycl. Chem. ¢ 1969), 6, p. 517; Gilman H., J. Am. Chem. Soc. 1955), 77, p. 6059th

Reaction scheme 17

H

In which

R ¹ to R ^s, map are the same as in the general description.

XS is S, O or MR ¹³

Ketones of formula IX can be prepared by general methods known in the art (or minor modifications thereof), see, for example, W. Flemming et al., Chem. Ber. (1925), 58, 1612; I. W. Still et al., Can. J. Chem. (1976) 54, 453-470; V. J. Trayrieli et al., J. Org. Chem. (1961), 26, 2728;

I. Nasuno et al., WO 94/08988; F. Camps et al., J. Heterocycl. Chem. (1985), 22 (5), p. 1421; Raas et al., Indian J.

Chem. B. (1985), 24 (11), p. 1159; S. Ghosh et al., Tetrahedron (1989), 45 (5), p. 1441; A. Danan et al., Synthesia-Stuttgart (1991), (10), p. 879; P. llagnus et al., J. Chem. Soc. Chem.

Comm. (1991), (7), p. 544; A. Padwa et al., J. Org.

(1989) 54 (12) p. 2862; S.A. Alla (1979), 44, p. 4213; J. B'lake et al., J. / Im. Chem. Soc. (1966),

88, p. 4061; 1. * 1 Llori et al., J. Chem. Soc. Chem. Comm. (1990), S. Kano et al., J. Chem. Soc., Perkins, p. 2105; A. F. Behkli et al., Khim

Geterotsikl. Soedin. (1975), p. 1118

Am. Chem. Soc. (1949), 71, p. 1901, J Chem. (1974) 39 (14), p. 2044; F.

Chem. Soc. (1957), p. 4166; A. C, Jain et al. Indian J.

B. (1987), 2Ei (2), p. 136; G. Ariamala et al., Tet.

(1988) 29 (28) p. 3487; B. loubinoux

Chem. Org. Chem.

(18), p. 1222; Submitted (1980),

W.

A.

G.

S. Johnson et al., J. Hlirsh et al., J. Org. I * lann et al., J. Org.

Chem.

et al.,

Lett. Tet. Let t.

(1992), 33 (16), p. 214

Cabiddu et al., J. Organomet

Chem. (1989). 366 (1-2), p. 1; R. HnasenKamp et al., Chem. Ber.

1980, 113, p. 1708; D. A. Pulman et al., J. Chem. Soc. Perkins 1st translation ¢ 1973), p. 410; W. C. Lumma et al., J. Org. Chem. ¢ 1969), 34, p. '1566; Clark, P. D. et al., Can. J.

Chem. (1982) 60 (3), p. 243rd

Thiokethores of formula X can be prepared from ketones of formula IX by conventional methods known in the art, see, for example, V. K. Lusis et al., Khim. Geterotslklt. ¢ 1986), (5), p. 709; T. A. Ghibisova et al., Zh. Org. Khim., 1986, 22 (9), p. Compounds of formula XI can be prepared by conventional methods known in the art, see, for example, U1. Adams et al., Chem. Ber. 1982, 115, p. 2592; 1. * 1

J. Dawson et al., J. Fled. Chem. (1984) 27 (11). p. 1516th

Compounds of formula (XII) may be prepared by conventional methods known in the art, see, for example, H. Ishibashi et al., J. Chem. Soc. Chem. Commun. ¢ 1988), (12), p. 827; L. Brandsma et al., Synthesis ¢ 1978), p. 577. Compounds of formula XIV may be prepared from ketones of formula IX by conventional methods known in the art, see for example 5579; A. 931-942; R

J. Hibino et al., Tet. Lett. ¢ 1985), 26

S. Rao, Synthetic Commun. ¢ 1989), 19 (45), p. 5-6), p.

G. Gentles et al., J. Chem. Soc. Perk. 1. translation ¢ 1.991), (6), p. 1.423; F.A. Davis, Tet. Lett. ¢ 1991), 32, (52), p. 7,671th

Compounds of formula XVI may be prepared by those skilled in the art from the debromoanalogues of compounds of formulas IX, X, XII, XIII and XV by the reactions and techniques described in Schemes 1.2 to 15. The dicarbonyl compounds of formula V are either commercially available or their it is possible: to prepare by conventional methods known in the art (or small modifications thereof), see for example D. Cartwright et al., EP 0283261-B1; J. Dangelo et al., Tet. Lett. (1991) 32 (26) p. 3063; T. Okado et al., J. Org. Chem. (1977) 42, p. 1163; B. E. Naryanoff et al., J. Am. Chem. Soc. 1975, 97, p. 3718; E. Er et al., Helv. Chim. Acta. 99 1.992), 75 (7), p. 2265; Y. 0. Vankar et al., Tet. Lett., 1987, 28 (5), p. 551; Pak, et al., Tet. Lett. (1991) 32

C 42), p. 6011; I. Nishiguchi et al., Chem. Lett. C1981), p. 551; B. Eistert et al., Liebigs et al. Chem. 1962), 659, p. 64;

Hamer, N.K., Tet. Years. ¢ 1986), 27 ¢ 19), p. 2167; 1. * 1 Sato et al., Heterocycles ¢ 1987), 26 ¢ 10), p.

Tet. Lett. ¢ 1995) 36 ¢ 2), p. 291; K. WITH. Lett. ¢ 1984), 25 ¢ 18) , p . 1871; h. Sat ¢ 1991), 47 ¢ 30). p. 5689; Π. Sato and al. ¢ 1990) 38 ¢ 1), p. 94; T. Meal, U. WITH. et al., U. S. 5 093 503rd

2611; A. Plurray et al., Kochhar et al., Tet. et al., Tetrahedron Chem. Pharm. Bull. 4, 931, 570; T. Nuel a

Compounds of formula Ib can be readily prepared by those skilled in the art using the reactions and techniques described in Schemes 18 through 21 of this section, as well as the following specific procedures given in Examples 2 and 4. Definitions of k, m, p, R ¹ -R ^s , R ^and -R 1 ^:> and X, are listed in the paragraph entitled Summary of the Invention.

Scheme 18 illustrates the preparation of compounds of formula Ib ¢ R ^L and R ^R do not form together with the carbon to which they are attached, CX = O) and C = S) and R ⁶³ = R ⁶³ *, wherein R ⁶³ ^ to identical to R ^B , as defined in the Summary of the Invention), but not a hydrogen atom), wherein the compound of the formula Ib ¢ R ¹ and R ^net do not form together with the carbon atom to which they are attached (CX = O) and CX = ^s), and R = H) is treated with a reagent of formula XVII in the presence of a base, wherein X represents ^a chlorine, bromine, fluorine, trifluoromethanesulfonate or acetate, and ^R '' is as defined above. This amalgamation is effected by conventional methods known in the art; see, for example, K. Nakamura et al., WCJ

95/04054.

Reaction scheme 18

Ib CR ¹ and together, on the bound, R ^C3 = H) R ² do not form with a carbon atom— Ib CR ¹ and R ² do not form together with the carbon atom to which they are attached which CC = 0) are on CC-S) + R ^ 'X ^ XVII bound, R ^S = H) CC = O) and CC = S) Reaction si chemistry 19 is a preparation of compounds of general formula formula Ib CR ¹ and R ² do not form spola with the atom carbon to which are bound, CC = O) and CC = S) a R ^S = H) at ester

of formula XVIII, CR ¹ and R ^{2 do not form} together with the carbon atom to which they are attached (CC = O) and CC = S)) react with a base such as triethylamine in the presence of a catalytic amount of a cyanide source (e.g. acetone cyanohydrin or potassium cyanide). This rearrangement is carried out by methods known in the art, see for example WJ Michael, EP 0369803-A1.

Reaction scheme 19

XVIII

CR ¹ and R ² do not form together with the carbon atom to which they are attached, CC = (i) and CC (S)) base C e.g. triethylamine) and a cyanide source in a catalytic amount of Cnapr. acetone cyanohydrin or potassium cyanide)

IN

Ib CR ³ and R ² do not form together with the carbon atom to which they are attached (CC = O) and CC = S)), Ρ ^θ -Η)

Reaction Scheme 20 illustrates the preparation of compounds of formula Ib (R ¹ and R ²² together with the carbon atom to which they are attached form C: (= O)) wherein the compound of formula 1b CR ¹ and R ² are independently an alkoxy group having 1 to ES or R ¹ and R ² together form-C) - (CH ₂ = R = O-) is stirred in an aqueous solution of hydrochloric or hydrobromic acid (<0.1 N to 12 M) at temperatures in the range of from 10 ° C to 100 ° C for 30 minutes to 3 days. This conversion is accomplished by methods known in the art (or minor modifications thereof), see, for example, PA Grieco et al., J. Am. Chem. Soc. (1977), 99, p. 5773; PA Grieco et al., J. Am. Chem. Soc. (1978) 43, p. 4178th

Reaction scheme 20 lb lb

R ¹ and R ² are independently C 1 -C 6, or R ^L and R ² do not form a n οροί - 0- _<p CH) _r. E) -)

CR ¹ and R ² together with the HCl / H ² O-carbon atom to which they are attached form C 0 = O) or HE 3r / H.

Esters of formula X9III (CR ¹ and R ² together with the carbon atom to which they are attached form C (= O) and C (= S)) can be prepared by reacting hydroxypyrazole of formula XIX with an acid chloride of formula 91 (R ¹ and R ² do not form together with the carbon atom to which they are attached, C (= O) and C (= S)) in the presence of a slight molar excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, dichloromethane or toluene at temperatures ranging from ⁰ ° C to 110 ° C (Reaction Scheme 21). This type of coupling is carried out by methods known in the art, see for example WJ Michael, EP 0369803-A1.

VI (R ¹ and R ²¹ do not together with the carbon atom to which the reaction scheme

RLO

XIX base

E.g., propylene glycol. triethylamine)> XVIII (R ¹ and R ² together with the carbon atom to which they are attached do not mean CC = O) and C (= S))

Compounds of formula (1c) can: easily be prepared from compounds of formula (Ia) (R ¹ and R ² together form: with the carbon atom to which they are attached, CC = O)) or Ib CR ¹ and R ² together with the atom the carbon to which they are attached (C (= O)) by treatment with P 2 S ₁₀ or Lawesson's reagent C (see Reaction Scheme 22). This conversion is carried out by conventional methods (known in the art (or small modifications thereof), see for example 709; T

V. K. Lusis a

A. Chibisova et al., Khim. Geterotsikl. C1986), et al., Zh. Or <3rd Khim. ¢ 1986), 22 C9), p. 2019. Protection and deprotection of certain functional groups of the starting materials of the general formula IA CR ¹ and R ² together with the carbon atom to which they are attached form C (= O)) or Ib CR ¹ and R ² together: with a carbon atom , bound,

The use

C (= 0)) can: be in and the choice of protective some case groups will not be for:

in the field of chemical synthesis present a problem that is necessary for those skilled in the art (see for example Organic Synthesis

T.

Second

W. Greene:

et al., Protective Groups in Edition; Wiley, New York, 1991).

in which they have k, m, p.

R ³ and R ^p, C and X are as defined in

R e: a c h a n d s 2 2

P ₄ S ₁₀ or Lewesson reagent 1a or Ib> 1c

CR ¹ and R ^ne do not together with the carbon atom to which they are attached, CC = 0))

It will be appreciated that some of the reagents described above and the reaction conditions for preparing the compounds of Formula I may not be compatible with certain functional groups present in the intermediates. These will help to obtain the desired products by incorporating deprotection of the functional group. The use of groups will not cause problems to those skilled in the art, see for example Greene T.W., LJuts, P.G. Protective Groups irt Organic Synthesis, 2nd edition; Wiley: N. York, 1991). It is also to be understood that in some cases, following the introduction of the reagent described in the individual schemes, it may be necessary to carry out other conventional protection cases and to select protective chemical syntheses that are not in the present invention related to the preparation the compounds of formula I described above. It should also be appreciated by those skilled in the art that in some cases it may be necessary to combine the steps described in the above schemes with respect to the order of steps used to prepare the compounds of Formula 1.

One of ordinary skill in the art would also appreciate that the compounds of Formula I and the intermediates described herein may be subjected to various electrophilic, nucleophilic, radical, organometallic, and reduction reactions to add certain substituents or modify existing substituents.

The invention can be practiced.

it will be appreciated by those skilled in the art that the invention may be fully embodied only on the basis of the above description

Accordingly, the following examples are illustrative only and are not intended to limit the scope of the invention as set forth in the appended claims. The percentages given in the following examples are to be understood as weight percentages, except for chromatographic solvent mixtures, or unless otherwise specified. Parts and percentages of chromatographic solvent mixtures are to be considered by volume unless otherwise specified. Abbreviation dec. indicates that the compound decomposes on melting. ¹ H NMR spectra are reported in ppm down from tetramethylsilane; s = slnglet, d = doublet, t = triplet, q = quadruplet, m ~ multiplet, br s = broad singlet.

DETAILED DESCRIPTION OF THE INVENTION

Example

Step n; Preparation of 3-E (4-bromophenyl) thiol propanoic acid

8.6 g (0.211 mol) of sodium hydroxide was added to water to which 20.0 was added to 45 ml of g (0.106 mol)

Bromothiopheno 1 by the Company) and the mixture (obtained from Aldrich Chemical) While the mixture was cooled to about 0 ^{° C>} C held at: below 5 ° C, 18.0 g (0.116 mol) was added portionwise. of 3-bromopropionic acid (obtained from Aldrich Chemical Company) The mixture was warmed to room temperature, stirred for 1 hour under nitrogen with diethyl ether (3 x 100 mL), the aqueous layer was HCl and filtered to give 27, 95 g of Step A in m.p. 101-103 ° C.

and then washed acidified by adding 1 N of the title compound from

NMR (COCl ₃ ): δ 2.66 (t, 2H), 3.14 (t, 2H), 7.2 (m, 2H), 7.4 (m, 2H).

Step B: Preparation of 6-bromo-2,3-dihydro-4 H -1-benzothiopyran-4-one

200 ml of concentrated sulfuric acid was added to 27.7 g

The mixture was stirred at room temperature under nitrogen overnight and then poured over crushed ice. The resulting mixture was filtered and the solid was dissolved in methylene chloride. The resulting solution was dried over anhydrous magnesium sulfate, filtered and evaporated to dryness to afford 14.77 g of the title compound of Step B as a solid, melting at 50 ° C (dec.).

^X CCDCls NMR): 3.0 8 m, 2H), 3.2 m, 2H), 7,1.6 to 8.2, C3H).

Step C; Preparation of 6-bromo-2,3-dihydrospiro C 4 H -1-benzothiophvran-4,2'-1,3,3-dioxole anu3

14.7 g (0.016 mol) of the title mol) of ethylene glycol C obtained by Company) and 0.4 g of C2.10 compound from Step B, 11 ml of CO, 19 from Aldrich Chemical mmol) p-toluenesulphonic acid monohydrate C obtained from from Aldrich Chemical Company) was added to 120 mL of toluene. The solution was boiled overnight with stirring under reflux and nitrogen and then washed with 1M sodium carbonate (2 x 250 ml) and then water (2 x 250 ml). The organic layer was dried over anhydrous sodium sulfate, filtered and evaporated to dryness to give 13.58 g of the title compound of Step C as an oil.

1 H NMR (CDCl ₃ ): δ 2, 2 Cm, 2H), 3.16 Cm, 2H), 4.1 Cm, 2H), 7.0-7

7.6 (C3H).

Step D:

Preparation of 2,3-dihydrospiro [4,7-l-benzothiopyrrole-4,2'-1,3,3-dioxolane] -6-carboxylic acid

13.58 g (0.047 mol) of the title compound from Step C was added to 150 mL of tetrahydrofuran and the solution was cooled to about -65 ° C and 23 mL was added dropwise to the solution while maintaining the temperature below -55 ° C. (0.057 mol) of 2.5M n-butyllithium in hexane C obtained from Aldrich Chemical Company). After 1 h stirring under nitrogen was added at once _{and the} excess solid C0 and the mixture to warm to room temperature and stirred overnight. Then, 100 mL of hexane was added to the mixture and the mixture was filtered. 500 m 3 was added to the solid residue. water and 400 ml of methylene chloride. The solution was cooled to approximately 0 ° C and acidified to pH 1 with concentrated hydrochloric acid and extracted with methylene chloride (3 x 400 mL). The resulting solution was dried over anhydrous magnesium sulfate, filtered and evaporated to dryness to give. 8.58 g of the title compound of Step D as a solid, melting at 186.7 ° C dec.).

^:, 1 R * H NI CMe-Asc.) - ^): 6 2.2 m, 2H), 3.2 m, 2H), 4.1 m, 4H), 7.2 to 8.0, C3H), 12.8 (br s, 1H).

Step E t Preparation of 1,3-Dioxide 2,3,3-dihydrospiroE 4 / 7-1-benzothiopyran-4,2 * -II, 33dloxolan] -6-carboxylic acid

8.5 g (0.034 mol) of the title compound of Step D and 41.5 g (51 mol) of sodium acetate were added to 160 ml of methanol. The suspension was cooled to about 0 ° C and a solution of 35.2 g (0.057 mol) of the company product was added dropwise to this mixture, which kept the temperature below 6 ° C. Aldrich Chemical Company, labeled (jXE) NO (potassium peroxymonosulfate) in 160 mL of water. The mixture was warmed to room temperature and stirred under nitrogen overnight. The mixture was acidified to pH 2 and diluted with 100 mL of water, cooled with concentrated acid, extracted with chloroform (3 x 200 mL) to approximately 6 ° C. The combined organic layers were dried over anhydrous magnesium sulfate, filtered and evaporated to dryness. The crude product was triturated with a mixture of hexane and diethyl ether (C19) to give 6.98 g of the title compound of Step E as a solid, melting at 208 ⁽ > 0 DEG C.).

^X H NMR CMe ^ SO ^): 6 2.6 m, 2H), 3.7 m, 2H), 4, 1 and 4.2 m, 4H), 7.9 to 8.15, C3H), 13 1.6 (br s, 1H).

Step E; Preparation of 1,3-Dioxide 2,3-dlhydrospiroC4 / 7-1-benzothiopyran-4,2'-11,33-dioxolane-6-carboxylate

2.0 g (7.0 mmol) of the title compound of Step E, 1.2 mL ¢ 0.014 drop mol) of oxalyl chloride (obtained from Janssen) and N, N-dimethylformamide were added to 59 mL of methylene chloride. The mixture was refluxed for 2 hours under nitrogen and then evaporated to dryness. To the residue was added 50 ml of methylene chloride and the resulting mixture was evaporated to dryness. To the residue was added another 50 mL of methylene chloride and the solution was cooled to approximately With 0 ^<:: ° C Approximately 0.86 g (7.7 mol) of 1,3-cyclohexanedione (obtained from Aldrich Chemical Company) and then 2.7 ml (0.0196 mol) of triethylamine were added and the mixture was warmed to room temperature while being heated to room temperature. the temperature was stirred overnight. The mixture was evaporated to dryness, the residue was stirred in 100 ml of water and filtered. The crude product was washed with hexane to give 2.19 g of the title compound of Step F as a solid, melting at: 1.85-186 ° C.

^l H NMR _(CDCl3) 6 2 t, 2 (m, 2H), 2.5 (t, 2H), 2.7 (t, 4H), 3.7 (m,

2H), 4.2 (m, 2H), 4.3 (m, 2H), 6.0 (s, 1H), 8.0-8.25 (3H).

Step G

Preparation of S, S-dioxide 2-6 (2,3-dihydrospiroE4, N-1-benzothiopyran-4,2'-61, 31dloxolanl-6-yl) carboriyl-1,3-cyclohexanedione

2.1 g (0.0056 mol) of the title compound of Step F, 4 drops of acetone cyanohydrin (obtained from Aldrich Chemical Company) and 1.36 ml (0.0097 mol) of triethylamine were added to 50 ml. acetonitrile and allowed to stir at room temperature for 3 hours: under nitrogen. The mixture was evaporated to dryness and 25 ml of water was added to the residue. The resulting mixture was acidified to pH 1 with concentrated hydrochloric acid and filtered. The crude product was dissolved in diethylene chloride and the resulting solution was dried over anhydrous magnesium sulfate, filtered and evaporated to dryness to give 1.5 g of the title compound of Step G, a compound of the invention as a solid melting at 131 °. '' C (dec.).

^x 1 HNMR (CDCl _3): 6 2.1 (m, 2H), 2,6i (m, 6H), 3,6i (m, 2H), 4.1 (m,

21-1), 4.2 (m, 2H), 7.6-7.9 (3H).

Example 2

Step A; Preparation of 1-Ethyl-1 H -pyrazol-5-yl-1,3-dihydrospiro [N-1-benzothiopyran-4,2'-1,3,3-dioxolane-6-carboxylate 1,1-dioxide

1.38 g (4.9 mmol) of the title compound of Step E from Example 1, 0.85 ml (0.0097 mol) of oxalyl chloride C from Janssen) and 2 drops of (R, N-dimethylformamide) were added to 50 ml of methylene chloride . The mixture was refluxed for 2 hours under nitrogen and then evaporated to dryness. To the residue was added 50 ml of methylene chloride and the resulting mixture was evaporated to dryness. An additional 50 mL of methylene chloride was added to the residue and the solution was cooled to approximately 0 ° C. Then approximately 0.60 g (5.4 mmol) of 1-ethyl-1 H -pyrazol-5-ol and then 1.9 ml (0.0136 mol) of triethylamine were added and the mixture was allowed to warm to room temperature while stirring. the temperature was stirred overnight. The mixture was evaporated to dryness, the residue was stirred in 100 ml of water and filtered. The crude product was washed with hexane to give 1.45 g of the title compound of Step A as a solid, melting at 158-160 ° C.

¹ H (IR (CDCl ₃ ): δ 1.4 (t, 3H), 2.7 (m, 2H), 4.1-4.3 (m, 6H),

6.2 (s, 1H), 7.5-8.3 (4H).

Step B: Preparation of S, S-dioxide (2,3-dihydrospiro [4A] -1-benzothiopyran-4,2'1,31-dioxolan-6-yl) -1-ethyl-5-hydroxy-1H-pyrazole-4 yl) methanone

1.43 g (0.0038 mol) of the title compound of Step A, 4 drops of acetone cyanohydrin (obtained from Aldrich Chemical Company) and 0.92 ml (0.0066 mol) of triethylamine were added to 50 ml of acetonitrile and allowed to stir overnight at room temperature. room temperature under nitrogen. The mixture was evaporated to dryness and 25 ml was added to the residue. water. The resulting mixture was acidified to pH 1 with concentrated hydrochloric acid and filtered. The crude product was washed with hexane and dissolved in methylene chloride, and the resulting solution was dried over anhydrous magnesium sulfate, filtered and evaporated to dryness to afford 0.44 g of the title compound of Step B, the compound of the invention, as an oil.

¹ H ^N 14 R CCDCl ₃ ) _S δ 1.46 (t, 3H), 2.7 cm (2H), 21-1), 3.7 cm (2H), 4.1 cm q,

2H), 4.2-4.3 (CM, 4H), 7.7-4.0 (C4H).

Example 3

Step n; Preparation of 3 - [(2,5-Dichlorophenyl) thio] propanoic acid

44.68 g (12.12 mol) of sodium hydroxide was added 240 ml of water, to which 100 g of CO, 56 mol (2,5-dichlorobenzenethiol (obtained from Aldrich Chemical Company) was added and the mixture was cooled to 10 ml. C. While maintaining the temperature below 25 ° C, 93.98 g (0.62 mol) of 3-bromopropionic acid (purchased from Aldrich Chemical Company) was added portionwise. The mixture was warmed to room temperature, stirred for 2 hours under nitrogen and then washed with diethyl ether (3 x 400 mL). The aqueous layer was acidified by addition of 1N HCl and filtered. The resulting residue was dissolved in 2 L of methylene chloride and 50 mL of methanol. The resulting solution was magnesium, filtered <

dried over anhydrous sulfate after evaporation to dryness yielded

126, 34 g of the title compound of Step A as a solid, melting at 99 ° C (dec.).

^LH NI4R CCDC1 _3): 6 2.75 t, 2H), 3.2 t, 2H), 7.1 to 7.3, C3H).

Step B

Preparation of 5,8-Dichloro-2,3-dihydro-4,7-l-benzothiopyran-4-one (CO, 2E) mol) of the title compound of Step A and 25.6 ml (0.35 mol) of thionyl chloride were added to 225 ml of chloroform, and the mixture was refluxed under nitrogen for 2 hours. The mixture was then concentrated and the resulting residue was dissolved in 75 ml of carbon disulphide and the resulting solution was added dropwise to a cooled CO (C) solution of 46.8 g (0.351 mol) of aluminum chloride in 200 ml of carbon disulphide while keeping the temperature below 5 '. ° C The mixture was refluxed for 1 hour under nitrogen and then stirred at 35 ° C for 2 days. The reaction mixture was poured into> 300 g of crushed ice containing 150 ml of concentrated hydrochloric acid and the resulting mixture was extracted with chloroform (3 x 200 ml). The combined organic layers were washed with 10% sodium hydroxide (2 x 150 mL), water (2 x 150 mL), dried over anhydrous magnesium sulfate, filtered and evaporated to dryness to afford 45.18 g of the title compound of Step B as a solid. , melting at 65-68 ° C.

1 H NMR (CDCl ₃ ): δ 3.8 (m, 2H), 3.3 (m, 2H), 7.1-7.35 (2H).

Step C; 6 - b reme - 5, 8 - d 1 c h 1 ó r - 2, 3 - d i h d r o - 4 H-1 - b o n t o o p in ran-4-one

A solution of 45.18 g (0.19 mol) / title compound of Step B in 400 mL of methylene chloride was added dropwise at room temperature and under nitrogen to a mixture of 64.6 g (0.4E <mol) of aluminum chloride in 400 mL of methylene chloride. . After stirring for 15 minutes, 10.5 ml (0.20 mol) of bromine was added dropwise and the mixture was refluxed for 10 minutes. The still warm mixture was poured into 550 g of ice containing 110 ml of concentrated hydrochloric acid and the resulting mixture was extracted with diethyl ether (2 x 500 ml). The combined organic layers were dried over anhydrous sodium sulfate, filtered and evaporated to dryness to give 57.37 g of the title compound of Step C as a solid, melting at 89-90 ° C.

^L 1 HNMR (CDCl ₃₎ 6 3.0 (m, 2H), 3.3 (m, 2H), 7.7 (s, 1H).

Step D; Preparation of 6-bromo-5,8-dichloro-2,3-dihydrospiro [4 H] -benzothiophvran-4,2'-1 ', 3] dloxolan] g (0.048 mol) of the title compound from Step C, 150 ml ethylene glycol, 100 ml dimethyl orthoformate (obtained from Aldrich Chemical Company) and 0.06 g of p-toluenesulfonic acid monohydrate were mixed together: overnight at 80 ° C and under nitrogen. The mixture was diluted with 250 mL of diethyl ether and washed with a mixture of 1 N sodium hydroxide and saturated aqueous sodium chloride (1: 1, 2 x 300 mL), saturated aqueous sodium chloride (1 x 500 mL), dried over anhydrous sodium sulfate, filtered and evaporated to dryness. . The crude product was purified using silica gel chromatography eluting with ethyl acetate: hexane (0.5: 9.5) to give 8.39 g of the title compound of Step D as a solid, melting at 152-153 ° C.

Ľ NMR (CDCl 3): δ 2.3 (m, 3H), 3.0 (m, 2H), 4.16 (τη, 2H), 4.37 (m, 2H), 7.6 (s, 1H) ).

Step E ': Preparation of 5,8-Dichloro-2,3-dihydrospiro [4F] -1-benzothiopyran-4,2'-Cl, 3'-dioxolane] -6-carboxylic acid

8.3 g (0.023 mol) of the title compound of Step D was added to 150 mL of tetrahydrofuran. The solution was cooled to about -65 ° C and while maintaining the temperature below -55 ° C, 11.2 mL (0.028 mol) of 2.51 * 1 n-butyllithium in hexane was added dropwise. After stirring for 30 minutes, carbon dioxide was bubbled into the mixture for 1 hour. The mixture was allowed to warm to room temperature. To this heated mixture was added 150 mL of hexane and the mixture was filtered. The solid was added to water and the resulting mixture was acidified to pH 1 by addition of concentrated hydrochloric acid and then extracted with methylene chloride (3 x 100 mL). The combined extracts were dried over anhydrous magnesium sulfate, filtered and evaporated to dryness to give 5.0 g of the title compound of Step E as an oil.

^X H NHR. (CDCl ₃ ): δ 2.3 (m, 2H), 3.0 (m, 2H), 4.16 (m, 2H), 4.38 (m, 2H), 7.7 and 7.8 ( 2s, 1H). N1R indicates the presence of approximately mol. % tetrahydrofuran remaining in the oil.

Step F; Preparation of 5,8-Dichloro-2,3-dihydrospiro [4,7- d] -1-benzothiopyran-4,2'-1,3,3-dioxolane-6-carboxylic acid 1,1-dioxide. and

5.0 g (0.0157 mol) of the title compound of Step E and 1.97 g (0.024 mol) of sodium acetate were added to 75 ml of methanol. The solution was cooled to approximately 0 ° C and a solution of 16.41 g (0.0267 mol) of OXONE (obtained from Aldrich Chemical Company) in 75 ml of water was added dropwise while keeping the temperature below 6 ^° C. The mixture was warmed to room temperature and stirred overnight under nitrogen. The mixture was diluted with 50 mL of water, cooled to approx. 0 ^<:> 0, acidified with concentrated hydrochloric acid to pH 1 and extracted with chloroform (3 x 150 mL). The combined organic layers were dried over anhydrous magnesium sulfate, filtered and evaporated to dryness to give 3.59 g of the title compound of Step F as a solid melting at rt. 165 ° C (dec.).

^, By NMR ^L H (L * _and S0 le-d _a) 6 = 2.6 (m, 2H), m, 2H), 9.0 (s, 1H).

3.7 (t, 2H), 4.18 (m, 2H), 4.3

Step G: Preparation of 3-Oxo-1-cyclohexen-1-yl-5,8-di-biphenyl-2,3-di-1-dioxide. C 4 / · / -1 - b e n t o o t y n - 4, 2 '- C1, 33-dioxolanl-6-carboxylate

1.75 g (4.97 mmol) of the title compound from Step F, 1.30 mL (0.015 mol) of oxalyl chloride (obtained from Jansen sen) and 2 drops of N, N-dimethylformamide were added to 50 mL of the title compound. ml of methylene chloride. The mixture was refluxed for 2 hours under nitrogen and then evaporated to dryness. To the residue was added 50 ml of methylene chloride and the resulting mixture was evaporated to dryness. An additional 50 mL of methylene chloride was added to the residue and the solution was cooled to approximately 0 ° C. Then approximately 0.61 g (5.5 mmol) of 1,3-cyclohexanedione (obtained from Aldrich Chemical Company) was added followed by 2.15 ml ¢ 0.0154 mol) of triethylamine and the mixture was stirred for 2 days. The mixture was evaporated to dryness and the crude product was purified by silica gel chromatography eluting with ethyl acetate / hexane (6: 4) to give 0.62 g of the title compound of Step B as a solid, melting at 168 ° C (dec.). .

^{Χ Η} NMR (CDC1 _3): In 2.1 m, 2H), 2.5 t, 2H), 2.7 C t, 4H), 3.6 m,

2H), 4.2 (m, 2H), 4.4 (m, 2H), 6.1 (c, 1H), 7.8 (c, 2H).

Step H: Preparation of S, S-Dioxide 2-1 (5,8-Dichloro-2,3-dihydrospiro [4- (7-l-benzothiopyridin-4,2'-yl, 3] dioxolan-6-yl) - carbonyl) -1,3-cyclohexanedione

0.60 g (1.3 mmol) of the title compound (Step G), 1 drop of acetone cyanohydrin (obtained from Aldrich Chemical Company) and 0.33 ml (2.4 mmol) of triethylamine were added to 50 ml of acetonitrile and passed through night; stir at room temperature; under nitrogen. Approximately 0.06 g of potassium cyanide was added to the mixture, evaporated to dryness and acidified to pH 1 and filtered, from step H, a melt, and stirred for 2 hours. The mixture obtained; water was added to the residue. Water grains; 1: 1: 1 to give 0.40 g of the title compound of the invention, as a solid

140 ° C dec.).

^X H by NMR CCDC1 _3): δ 2.0 m, 2H), 2.6 m, 6H), 3.6 m, 2H), 4.1 m,

2H), 4.35 (m, 2H), 7.2 (1H). NI * 1F3 indicates the presence of approximately 33 mol. % triethylamine remaining in the solid.

Example 4

Step A: Preparation of 3- (2,5-diinophenyl) thio] propanoic acid

43.4 g (1.086 mol) of sodium hydroxide was added to 230 ml of water, to which 75.0 g (0.543 mol) was then added

2,5-dimethylthiophenol (obtained from Aldrich Chemical Company) and a mixture; was cooled to approximately 10 ° C. While the mixture was kept at a temperature; below 25 ° C, 91.30 g (0.597 mol) of 3-bromopropionic acid (obtained from Aldrich Chemical Company) was added portionwise. The mixture was warmed to room temperature, stirred for 2 hours under nitrogen and then washed with diethyl ether (3 x 500 mL). The aqueous layer was acidified by the addition of 1M HCl and filtered to afford 112.79 g of the title compound of Step A as a solid, melting at 97-98 ° C.

@ 1 H NMR (CDCl3): .delta. 2.3 (s, 3H), 2.34 (s, 3H), 2.68 (t, 2H), 3.1 (t, 2H), 6.9 (d, 1H) 7.06 to 7.14 (2H).

Step B: Preparation of 2,3-dihydro-5,8-dimethyl-46H-1-benzopyran-4-one

530 ml of concentrated sulfuric acid was added to 24, 91 g (0.119 mol) of the title compound of Step A, which was cooled with an acetone-ice bath. The ice bath was removed, the mixture was stirred for 1 hour and then poured over crushed ice. The aqueous mixture was extracted with a mixture of dimethyl ether and hexane (1: 9, 6x)

500 mL), dried over anhydrous magnesium sulfate, filtered and evaporated to dryness to give 1.75 g of the title compound of Step B as an oil.

^X 1 HNMR (CDCl _3): 6 2.3 (s, 2H), 6.9 and 7.1 (2H).

3H);

2.6 (s, 3H), 2.97 (m, 2H), 3.2 (m,

Step C; Preparation of 6-bromo-2,3-dihydro-5,6-climethyl-4,7-l-benzothiopyran-4-one

A solution of 4.07 g (0.021 mol) of the title compound of Step B in 25 ml of methylene chloride was added dropwise to a mixture of 7.07 g (0.053 ml of methylene chloride), followed by 1.14 ml (0.022 mol) of aluminum chloride and 25 ml. Stirring was continued dropwise with bromine for one minute, and the mixture was refluxed for 10 minutes. The still warm mixture was poured into 10 ml of concentrated hydrochloric acid containing 75 g of ice, stirred for 10 minutes, diluted with 50 ml of water and then extracted with diethyl ether (2 x 200 ml). The combined organic layers were washed with water (2 x 200 mL), dried over anhydrous sodium sulfate, filtered and evaporated to dryness to give the crude product which was purified by chromatography on silica gel using ethyl acetate / hexane (5%: 95%). and gave 2.26 g of the title compound of Step C as a solid, melting at 87-88 ° C.

¹ H NMR (CDCl ₃ ): δ 2.3 (s, 2H), 7.45 (s, 1H).

3H);

2.6 (s, 3H), 3.0 Cm, 2H), 3.2 Cm,

Step D; Preparation of 6-bromo-2,3-dihydro-5,8-dimethylspiro [4 H] -1-benzothiopyran-4,2'-1,3 '] dioxolane]

26.06 g (0.096 mol) of the title compound of Step C, 250 mL

170 ml of trimethyl orthoformate (obtained from Aldrich Chemical Company) and 0.06 g of p-toluenesulfonic acid monohydrate were stirred together at 80 ° C and under nitrogen overnight. The mixture was diluted with 400 mL diethyl ether and washed with a mixture of 1 M sodium hydroxide and saturated aqueous sodium chloride (1: 1, 2 x 600 mL), saturated aqueous sodium chloride (1 x 600 mL). The organic layer was dried over anhydrous sodium sulfate, filtered and evaporated to dryness. The crude product was purified using silica gel chromatography eluting with ethyl acetate / hexane (1: 9) to give 24.73 g of the title compound of Step D as a solid, melting at 97 ° C (dec.).

^Α Η M 1 R (CDCl ₃ ): δ 2.2 (s, 3H), 2.3 (m, 2H), 2.4Cs, 3H), 3.0Cm,

2H), 4.15 (m, 2H), 4.3 (m, 25H). 7.3 (s, 1H).

Step E: Preparation of 2,3-dihydro-5,8-dimethylspiroE 4 / 7-1-benzothiopyran-4,2'-1,1,3-dioxolane-6-carboxylic acid

24.73 g (0.078 mol) of the title compound of Step D was added to 150 mL of tetrahydrofuran. The solution was cooled under nitrogen to about -70 ^° C and while maintaining the temperature below -65 ° C, 37.68 ml (0.094 mol) of 2.5 µl n-butyllithium in hexane was added dropwise. After stirring for 1 hour, carbon dioxide was bubbled into the mixture for 2 hours. The mixture was allowed to warm to room temperature. To the heated mixture was added 300 mL hexanes and the resulting mixture was filtered. The solid was added to a mixture of water and methylene chloride (400 mL: 400 mL), cooled to approximately 0 ° C, and acidified to pH 1 by addition of concentrated hydrochloric acid. The layers were separated and the aqueous layer was diethyl ether (2 x 300 mL). The combined organic layers over anhydrous magnesium sulfate were filtered and dried to give 4.73 g of the title compound of Step E in a melting point at 207-208 ° C.

0-d _&): 8 2.2 (m, 5H), 2.4 s, 3H), 3.0 m, 2H), 4.1 extracted was dried evaporated to a solid ¹ H NMR CMe ₂ S and 4.2 (m, 4H),

7.4 (s, 1H).

Step F; Preparation of 2,3-dihydro-5,8-dimethylspiro [4,7-l-benzothiopyran-4,2'-1,3,3-dioxolane] -6-carboxylic acid 1,1-dloxide

4.73 g (0.017 mol) of the title compound from Step E and 2.0 (0.025 mol) sodium acetate were added to 85 ml of methanol. The solution was cooled to about 0 ° C and a solution of 17.66 g (0.029 mol) of OXONE (obtained from Aldrich Chemical Company) in 85 ml of water was added dropwise while maintaining the temperature below 6 ° C. The mixture was warmed to room temperature and stirred under nitrogen overnight. The mixture was diluted with 50 mL of water, cooled to about 0 ° C, acidified with concentrated hydrochloric acid to about pH 2, and extracted with chloroform (3 x 150 mL). The combined organic layers were dried over anhydrous magnesium sulfate, filtered and evaporated to dryness to give 4.18 g of the title compound of Step F as a solid melting at 185 ° C dec.).

^X H NMR (He ₂ SO-d _&): 8 2.35 s, 3H), 2.5 m, 2H), 2.6 s, 3H), 3.5

(M, 2H), 4.16 (m, 2H), 4.2 (m, 2H), 7.6 (c, 2H).

Step G; Preparation of 1,1-Dioxide 1-ethyl-1H-pyrazol-5-yl-2,3-dihydro-5,8-dimethylspiroC4 / 7: 1-benzotlopvran-4,2'-1,3'-dioxolari-6-ol -carboxylate

1.18 g of C3, 8 mmol) of the title compound of Step F,

0.99 ml (0.0101 mol) of oxalyl chloride (obtained from Janssen) and a drop of (N, N-dimethylformamide) were added to 50 ml of methylene chloride.

The mixture was refluxed for 2 hours under nitrogen and then evaporated to dryness. To the residue was added 50 ml of methylene chloride and the resulting mixture was evaporated to dryness. An additional 50 mL of methylene chloride was added to the residue and the solution was cooled to approximately 0 ° C. Then approximately 0.51 g (4.5 mmol) of 1-ethyl-1H-pyrazol-5-ol and then 1.63 ml (0.012 mol) of triethylamine were added and the mixture was stirred over room temperature. night. The mixture was evaporated to dryness and the crude product was purified by silica gel chromatography eluting with ethyl acetate / hexane (6: 4) to give 0.24 g of the title compound of Step G as a semi-solid.

¹ H (CDCl 3): δ 1.4 (t, 3H), 2.5 (s, 3H), 2.6 (m, 2H), 2.8 (s,

3H), 3.5 (m, 2H), 4.1-4.4 (m, 6H), 6.26 (s, 1H), 7.5-7.7 (2H).

Step H: Preparation of 2,3-Dihydro-5,8-dimethylspiroC4,7-benzothiopyran-4,2'-1,33-diol-3-ol-6-yl S, S-dioxide (1-ethyl-5-hydroxy) 1- (7-pyrazol-4-yl) methane

0.24 g (0.59 mmol) of the title compound of Step G, 0.25 drops of acetone cyanohydrin (obtained from Aldrich Chemical. Company) and 0.14 ml (1.0 mmol) of triethylamine were added to 25 ml of acetonitrile and the mixture was allowed to warm to room temperature. under nitrogen.

The mixture was allowed to stir for 1.5 hours at room temperature. To the mixture was added approximately 0.06 g of potassium cyanide and the mixture was stirred overnight at room temperature. room temperature. The resulting mixture was evaporated to dryness and water was added to the residue. The aqueous mixture was acidified to pH 1 with concentrated hydrochloric acid and extracted with methylene chloride (2 x 50 mL): The combined organic layers were dried over anhydrous magnesium sulfate, filtered and evaporated to dryness to give 0.17 g of the title compound from step H, of the compound of the invention, as a solid, melting at 111 ° C (dec.).

¹ H NMR (CDCl ₃ ): δ 1.46 (t, 3H), 2.3 (s, 3H), 2.6 (m, 2H), 2.8 (s, 3H), 3.5 ( m, 2H), 4.1 (g, 2H), 4.2-4.3 (m, 4H), 7.3 (2H).

Example 5

Step A ·. Preparation of 3-oxo-1-cyclohexen-1-yl 2,3-dihydro-5,8-dimethylethyl 1,1-dioxide C 4 A 7-1-benzo [11] pyrimidin-4, 2 '- ,1,3 Z dioxoanil] -15-carboxylate

3.0 g (6 mmol) of the title compound of Step I-Example.

2, 5

M.J.

C 0.029 m o 1) o x and 1 y 1 o h 1 o r j. d u C o s c o n e n o o s o o o n o n s

Janssen) and 2 drops of N, N-dimethylformamide βει were added to 100 ml of methylene chloride. The mixture was refluxed for 2 hours under nitrogen and then evaporated to dryness.

100 mL of methylene chloride and the resulting mixture

Dryness was added to the residue.

To the residue was evaporated to an additional 100 mL of methylene chloride and the solution was cooled to approximately 0 ° C. Then approximately

1, 19

(0. 0106 mmol)

1,3-cyclohexanedione C obtained from Aldrich Chemical Company) and then 4.1b mL (0.030 mol) by simultaneous heating to a crude product with triethylamine and stirred overnight at room temperature. The mixture was evaporated to dryness, purified by chromatography over silica gel, eluting with ethyl acetate: hexane (1: 1) to give 1.33 g of the title compound of Step A as a solid, melting at 109-111.

^l H NMR <CDC1 ₃ ): 6 2, 1 cm. 2H); 2.5 Cm, 5H), 2, 6 cm. 2H); 2, 7 cm. 2H) , 2, 8 <s, 3H); 3, 5 cm. 2H); 4.2 C m, 214), 4, 3 C m. 214), 6, 0 C s, 1H) , 7, 8 (p. 1H), 7, 7 C s, 1H).

Step B: 3-Oxo-1-Oxy-1-hexyl-1,3-dihydro-5,8-dimethyl-spiroC4 H - 1-benzothiopyran-4,2-dioxide, S, S-dioxide 1 '- (1,3-Dimloxolan-1'-6-yl) -carbonyl-1,3-cyclohexanedione

1.33 g (3.3 mmol) of the title compound of Step A, 1 drop of a-o-ethoxy cyanohydrin (obtained from Aldrich Chemical Company) and 0.80 ml (5.7 mmol) of triethylamine were added to 50 ml of acetonitrile and allowed to stir for 1 hour. 5 hours. Approximately 0.06 g of potassium cyanide was added to the mixture, and the mixture was allowed to stir overnight at room temperature and under nitrogen. Then an additional 0.03 g of potassium cyanide was added to the mixture and stirred for an additional 3 hours. The resulting mixture was evaporated to dryness and water was added to the residue. The aqueous mixture was acidified to pH 1 with concentrated hydrochloric acid and filtered to give a solid residue which was dissolved in methylene chloride and the resulting solution was dried over anhydrous borate sulfate, filtered and evaporated to dryness to give 1.0 g of the title compound from step B, i.e. the compound of the invention, as a solid melting at 130 ° C (dec.).

^1H NMR CCOC1 ₃₎ S = 2.0 m, 2H), 2.2 s, 3H), 2.6 m, 6H), 2.7 s,

3H), 3.5 (m, 2H), 4.14 (m, 2H), 4.26 (m, 2H), 6.9 (1H).

Example 6

Preparation of 6-Bromo-2,3-dihydro-5,8-dimethylspirol-4 / 7-1-benzotlopyran-4,2'-11,31-dloxolane

To a solution of the title compound of Step C from Example 4 (5.0 g, 18.4 mmol) in methylene chloride (50 mL) was added 1,2-ethanedithiol (Aldrich, 2.32 mL, 27.7 mmol) under nitrogen. boron trifluoride diethyl etherate (Janssen Chimica, 3.4 mL, 27.7 mmol).

The resulting mixture was stirred overnight at room temperature. To this reaction mixture was added 1.0 N sodium hydroxide (5 mL) and saturated aqueous sodium chloride (50 mL). The resulting mixture was extracted three times with diethyl ether. The combined organic extracts were dried over anhydrous magnesium sulfate, filtered and concentrated to dryness under reduced pressure. The resulting residue was crystallized from

1-chloro butane gave the title compound of Step A (4.0 g) as a solid melting at 141-143 ° C.

0-1 NMR (COCl ₃ ): δ 2.19 C, 3H), 2.78 (m, 2H), 2.80 (s, 3H), 3.09 (m, 2H), 3.45 to 3.70 (C4H), 7.29 (s, 1H).

Step B; Preparation of 2,3-dihydro-5,8-dimethylspirol [4,7] -benzo-thiopyridine-4,2,2'-1H. 1, 3 J d i o x o 1 a n J - 6 - k a r b o x v 1 o

To a solution of the title compound of Step A (2.7 g, 7.7 mmol) in tetrahydrofuran (20 mL) under a nitrogen atmosphere cooled to

-78 ‘-’C drop by drop, while maintaining. temperature below -60 ° C, tert -butyllithium (Aldrich, 4.6 mL, 11.5 mmol of a 2.5 L solution in hexane) was added. After stirring for 2 hours, it was added. excess carbon dioxide (dry ice). The resulting mixture was allowed to warm to room temperature overnight at this temperature. To this reaction mixture was added hexanes (30 mL) and the mixture was filtered. The solid was added to a mixture of water and methylene chloride (20 mL: 20 mL), and the mixture was cooled to 0 ° C and acidified with concentrated hydrochloric acid to pH 1. The organic layer was separated and the aqueous layer was extracted diethyl ether (3 x 25 mL). The combined organic layers were dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to about 10 mL. A white solid precipitated and was isolated by filtration to give the title compound of Step B (1.62 g) as a solid, melting at 236-238 ° C.

Δ-1 NMR Cl ₂ SO-d ₆ ) δ 2.17 (s, 3H), 2.68 (m, 2H), 2.81 (s, 3H),

3.11 (m, 21-1), 3.50-3.70 (4H), 7.33 (S, 1H), 12.78 (s, 1H).

Step C: Preparation of 3-oxo-1-cyclohexen-1-yl 2,3,3-dihydro-b, 8-dimethyls piro E 4 / 7-1-benzothiophvran-4 ', 2'-1', 3, 3-dioxoan and 3 - 6 - • carboxylate of the compound of Step B (0.77 g, 2.4 mmol) in 0, 63 mL, 7.2 mmol was added under a nitrogen atmosphere and boiled 1 drop for 1.5 hours under

To a solution of the title methylene chloride (25 ml) and xyll (1, 1, 1, 2, 4, 6, 6-dimethylformamide),

The resulting mixture was refluxed and then evaporated to dryness. The resulting solution was added to the residue and the solution was cooled to approximately 0 ° C. To this mixture was added 1,3-cyclohexanedione mmol.) Followed by triethylamine (1.0 mL, 7.2 (Aldrich, 0.30 g, 2.6 mmol). The mixture was stirred overnight while maintaining room temperature. Saturated aqueous sodium chloride was added to the reaction mixture, and the resulting mixture was extracted three times with diethyl ether The combined organic extracts were dried over anhydrous magnesium sulfate, filtered, and concentrated to dryness under reduced pressure Chromatography of the crude product on silica gel, eluting with hexanes and ethyl acetate (3: 1) gave the title compound of Step C (0.96 g) as a semi-solid.

1 H NMR (CDCl ₃ ): δ 2.13 (m, 2H), 2.26 (s, 3H), 2.45 (t, 2H), 2.66 (m, 2H), 2.76 (m, 2H) 2.95 (s, 3H); 3.18 (m, 2H), 3.50-3.70 (4H), 6.00 (s, 111), 7 110 (s, 111).

Step D:

Preparation of 2-L (2,3-dihydro-5,8-dimethylspiro [4,7] -benzothiopyrano-4,2 '- E 1,3,3-dioxolane] -6-carbonyl 11' - 3-hydroxyethyl 2-cyclohexen-1-one

To a solution of the title compound of Step C (0.67 g, 1.6 mmol) in <12 mL) under a nitrogen atmosphere was added acetone cyanohydrin (Aldrich, 2 drops) and triethylamine (0.40 mL, 2.8 mmol). The mixture was allowed to stir overnight at room temperature. Then about 5 mg of potassium cyanide was added to the reaction mixture. After stirring for six hours, the mixture was heated to 50-55 ° C and held at this temperature for an additional 10 hours. After this time, the mixture was again cooled to room temperature and then concentrated under reduced pressure to water (20 mL) and the resulting dryness. To the resulting residue, the aqueous mixture was acidified to pH 1 with concentrated hydrochloric acid. The solid that separated from the mixture by filtration was an 80:20 mixture (0.60 g) of the title compound of Step D and the title compound of Step B as a solid, melting at 217-222 ° C.

¹ H NMR 2.20 (s, (m, 2H) (CDCl ₃ ) for the title 3H), 2.42 (t, 2H), 3.42-3.60 (4H), Step D compound: 6 2 0.03 (m, 2.66 (s, 3H), 2.72 to 2.81 (4H)

6.71 (s, 1H)

2H);

3, 16

The compounds which can be prepared in the following Tables 1 to 9 are using the methods described herein and methods well known in the art. In the tables of the abbreviation: n = normal, p = para, p-tolyl the following = 4-methylphenyl and NO- are used. = nitro.

_r 3j _R 3b

rl

H

H

H

H

H

H

H

H

H

H

H

H

-OCH ₂ CH ₂ OCH ₂ O-CH _{2 O-OCH2 CH2 OCH2} O _{CH2 OCH2} O _{CH2 OCH2} O _{CH2 OCH3 CH3}

H

Cl

Cl

Cl ch ₅

H

H

Cl

H

CH ₃

OH

OH

OH

OH .OH

OH ₂ • 2 ₂

Η H -OCH ₂ CH ₂ O- no ₂ H OH 2 1 ch ₃ ch ₃ -OCH ₂ CH ₂ O · ch ₃ ch ₃ OH ₂ 1 ch ₃ ch ₃ -OCH ₂ CH ₂ O- ch ₃ H OH 2 1 ch ₃ ch ₃ -och ₂ ch ₂ o- H H OH ₂ 1 ch ₃ ch ₃ -OCH2CH2. Cl Cl OH 2 1 ch ₃ CH ₃ • OCH ₂ CH ₂ O- Cl H OH 2 1 ch ₃ ch ₃ -OCH ₂ CH ₂ O- Cl ch ₃ OH 2 1 ch ₃ H -och ₂ ch ₂ o- ch ₃ CH3 OH 2 1 ch ₃ H -och ₂ ch ₂ o- ch ₃ H OH 2 1 ch ₃ H -och ₂ ch ₂ o- H H OH 2 1 ch ₃ H -och ₂ ch ₂ o- Cl Cl OH 2 1 ch ₃ H -och ₂ ch ₂ o- Cl H OH 2 1 ch ₃ H -och ₂ ch ₂ o- Cl CH ₃ OH 2 1 H H -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ OH 2 1 H H -OCH ₂ CH (CH ₃ ) O - ch ₃ H OH 2 1 H H -OCH ₂ CH (CH ₃ ) O - H H OH 2 1 H H -OCH ₂ CH (CH ₃ ) O - Cl Cl OH 2 1 H H -OCH ₂ CH (CH ₃ ) O - Cl H OH 2 1 H H -OCH ₂ CH (CH ₃ ) O - Cl CH ₃ OH 2 1 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ OH 2 1 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - ch ₃ H OH 2 1 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - H H OH 2 1 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - Cl Cl OH 2 1 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - Cl H OH 2 1 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - Cl ch ₃ OH 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ OH 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) O - ch ₃ H OH 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) O - H H OH 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) O - Cl Cl OH 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) O - Cl H OH 2 1 ch ₃ H OCH ₂ CH (CH ₃ ) O- Cl ch ₃ OH 2 1 H H -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ OH 2 1 H H -och ₂ ch ₂ ch ₂ o- ch ₃ H OH 2 1 H H -och ₂ ch ₂ ch ₂ o- H . H OH 2 1 H H -och ₂ ch ₂ ch ₂ o- Cl Cl OH 2 1 H H -och ₂ ch ₂ ch ₂ o- Cl H OH 2 1 H H -och ₂ ch ₂ ch ₂ o- Cl ch ₃ OH 2 1 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ OH 2 1

ch ₃ ch ₃ -OCH ₂ CH ₂ CH ₂ - ch ₃ H OH 2 CH ₃ -och ₂ ch ₂ ch ₂ o- H H OH 2 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- Cl Cl OH T ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- Cl H OH ₂ ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- Cl ch ₃ OH ₂ ch ₃ H -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ OH 2 ch ₃ H -och ₂ ch ₂ ch ₂ o- ch ₃ H OH ₂ ch ₃ H -och ₂ ch ₂ ch ₂ o- H H OH 2 ch ₃ H -och ₂ ch ₂ ch ₂ o- Cl Cl OH 2 ch ₃ H -och ₂ ch ₂ ch ₂ o- Cl H OH 2 ch ₃ H -och ₂ ch ₂ ch ₂ o- Cl CH 3 OH 2 H H ch ₃ o ch ₃ o ch ₃ ch ₃ OH 2 H H ch ₃ o ch ₃ o ch ₃ H OH 2 H H ch ₃ o ch ₃ o H The OH ₂ H H ch ₃ o ch ₃ o Cl Cl OH 2 H H ch ₃ o ch ₃ o Cl H OH 2 H H ch ₃ o ch ₃ o Cl ch ₃ OH 2 ch ₃ ch ₃ ch ₃ o ch ₃ o ch ₃ CH OH 2 ch ₃ ch ₃ ch ₃ o ch ₃ o ch ₃ H OH 2 ch ₃ ch ₃ ch ₃ o ch ₃ o H H OH ₂ ch ₃ ch ₃ ch ₃ o ch ₃ o Cl Cl OH 2 ch ₃ ch ₃ ch ₃ o ch ₃ o Cl H OH 2 ch ₃ ch ₃ ch ₃ o ch ₃ o Cl CH; OH 2 ch ₃ H ch ₃ o ch ₃ o ch ₃ CH. OH 2 ch ₃ H ch ₃ o ch ₃ o ch ₃ H OH 2 ch ₃ H ch ₃ o ch ₃ o H H OH 2 ch ₃ H ch ₃ o ch ₃ o Cl Cl OH 2 ch ₃ H ch ₃ o ch ₃ o Cl H OH 2 ch ₃ H ch ₃ o ch ₃ o Cl ch ₃ OH 2 H H h ₅ c ₂ oh ₅ c ₂ o CH ₃ CH; OH 2 H H h ₅ c ₂ oh ₅ c ₂ o ch ₃ H OH 2 H H h ₅ c ₂ oh ₅ c ₂ o H H OH 2 H H h ₃ c ₂ oh ₅ c ₂ o Cl Cl OH 2 H H h ₅ c ₂ oh ₅ c ₂ o Cl H OH 2 H H h ₅ c ₂ oh ₅ c ₂ o Cl CK ₃ OH 2 ch ₃ ch ₃ h ₅ c ₂ oh ₅ c ₂ o ch ₃ CH; OH 2 ch ₃ ch ₃ h ₅ c ₂ oh ₅ c ₂ o ch ₃ H OH 2 ch ₃ ch ₃ h ₅ c ₂ oh ₅ c ₂ o H H OH 2

CH ch ₃ h ₅ c ₂ oh ₅ c ₂ o Cl Cl OH 2 1 ch ₃ ch ₃ h ₅ c ₂ oh ₅ c ₂ o Cl H OH ₂ 1 ch ₃ ch ₃ h ₅ c ₂ oh ₅ c ₂ o Cl ch ₃ OH T l ch ₃ H h ₅ c ₂ oh ₅ c ₂ o ch ₃ ch ₃ OH n 1 ch ₃ H h ₅ c ₂ oh ₅ c ₂ o ch ₃ H OH ₂ .1 ch ₃ H h ₅ c ₂ oh ₅ c ₂ o H H OH 2 1 ch ₃ H h ₅ c ₂ oh ₅ c ₂ o Whose Cl OH ₂ 1 ch ₃ H H ₅ C ₂ OH ₅ C ₂ O Cl H OH 2 1 ch ₃ H h ₅ c ₂ oh ₅ c ₂ o Cl ch ₃ OH ₂ 1 H H -ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ ch ₃ OH 2 1 H H -ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ H OH 2 1 H H -ch ₂ ch ₂ ch ₂ ch ₂ - H H OH 2 1 H H -ch ₂ ch ₂ ch ₂ ch ₂ - Cl Cl OH 2 1 H H -ch ₂ ch ₂ ch ₂ ch ₂ - Cl H OH 2 1 H H -ch ₂ ch ₂ ch ₂ ch ₂ - Cl ch ₃ OH 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ CK ₃ OH 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ H OH 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ - H H OH 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ - Cl Cl OH 2 1 ch ₃ ch ₃ -CH ₂ CH ₂ CH ₂ CH ₂ - Cl H OH 2 1 ch ₃ CH 3 -ch ₂ ch ₂ ch ₂ ch ₂ - Cl CH ₃ OH 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ ch ₃ OH 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ H OH 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ - H H OH 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ - Cl Cl OH 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ - Cl H OH 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ - Cl ch ₃ OH 2 1 H H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ ch ₃ OH 2 1 H H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ H OH 2 1 H H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - h H OH 2 1 H H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - Cl Cl OH 2 1 H H -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - Cl H OH 2 1 H H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - Cl CK ₃ OH 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ CH _ľ , OH 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ H OH 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - H H OH 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - Cl Cl OH 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - Cl H OH 2 1

ch ₃ ch ₃ -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ · ci ch ₃ OH 2 CH H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ · ch ₃ ch ₃ OH 2 ch ₃ H -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - ch ₃ H OH 2 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ · H H OH 2 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - CI CI OH 2 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - CI H OH 2 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - CI CH ₃ OH 2 H H -ch ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ OH 2 H H -ch ₂ ch ₂ ch ₂ o- ch ₃ H OH 2 H H -ch ₂ ch ₂ ch ₂ o- h H OH 2 H H -ch ₂ ch ₂ ch ₂ o- ci CI OH 2 H H -ch ₂ ch ₂ ch ₂ o- CI H OH 2 H H -ch ₂ ch ₂ ch ₂ o- CI CH; OH 2 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- ch ₃ CK; OH 2 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- ch ₃ H OH 2 ch ₃ CH ₃ -ch ₂ ch ₂ ch ₂ o- h H OH 2 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- CI CI OH 2 ch ₃ CH ₃ -ch ₂ ch ₂ ch ₂ o- CI H OH 2 ch ₃ CH ₃ -ch ₂ ch ₂ ch ₂ o- CI CH ₃ OH 2 ch ₃ H -ch ₂ ch ₂ ch ₂ o- ch ₃ ch ₅ OH 2 ch ₃ H -ch ₂ ch ₂ ch ₂ o- ch ₃ H OH 2 ch ₃ H -ch ₂ ch ₂ ch ₂ o- H H OH 2 ch ₃ H -ch ₂ ch ₂ ch ₂ o- CI Cl OH 2 ch ₃ H -ch ₂ ch ₂ ch ₂ o- ci H OH 2 ch ₃ H -ch ₂ ch ₂ ch ₂ o- CI CH ₃ OH 2 H H -och ₂ ch ₂ o- ch ₃ ch ₃ OH 2 H H -och ₂ ch ₂ o- ch ₃ H OH 2 H H -och ₂ ch ₂ o- H H OH 2 H H -och ₂ ch ₂ o- ci CI OH 2 H H -och ₂ ch ₂ o- ci H OH 2 H H -och ₂ ch ₂ o- ci ch ₃ OH 2 ch ₃ ch ₃ -OCH ₂ CH ₂ O- ch ₃ CH; OH 2 ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ H OH 2 ch ₃ ch ₃ -och ₂ ch ₂ o- h H OH 2 ch ₃ ch ₃ -och ₂ ch ₂ o- ci Cl OH 2 ch ₃ ch ₃ -och ₂ ch ₂ o- ci H OH 2 ch ₃ ch ₃ -och ₂ ch ₂ o- CI ch ₃ OH • 2 ch ₃ H -och ₂ ch ₂ o- ch ₃ CH; OH 2

ch ₃ H -och ₂ ch ₂ o- ch ₃ H OH 2 0 ch ₃ H -OCH ₂ CH ₂ O- H H OH ₂ 0 ch ₃ H -OCH ₂ CH ₂ O- Cl Cl OH n 0 ch ₃ H -och ₂ ch ₂ o- Cl H OH ₂ 0 ch ₃ H -och ₂ ch ₂ o- Cl ch ₃ OH 2 0 H H -OCH ₂ CH (CH ₃ ) O - CH OH 2 0 H H -och ₂ ch <ch ₃ ) o- ch ₃ H OH 2 0 H H -OCH ₂ CH (CH ₃ ) O - H H OH 2 0 H H -OCH ₂ CH (CH ₃ ) O - Cl Cl OH 2 0 H H -OCH ₂ CH (CH ₃ ) O - Cl H OH 2 0 H H -OCH ₂ CH (CH ₃ ) O - Cl ch ₃ OH 2 0 ch ₃ CH ₃ -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ OH 2 0 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) 0 - ch ₃ H OH 2 0 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - H H OH 2 0 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - Cl Cl OH 2 0 ch ₃ CH -OCH ₂ CH (CH ₃ ) O - Cl H OH 2 0 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - Cl ch ₃ OH 2 0 CH3 H -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ OH 2 0 ch ₃ H -OCH ₂ CH (CH ₃ ) O - ch ₃ H OH 2 0 ch ₃ H -OCH ₂ CH (CH ₃ ) O - h H OH 2 0 ch ₃ H -OCH ₂ CH (CH ₃ ) O - Cl Cl OH 2 0 ch ₃ H -OCH ₂ CH (CH ₃ ) O - Cl H OH 2 0 CH 3 H -OCH ₂ CH (CH ₃ ) O - Cl ch ₃ OH 2 0 H H -OCH ₂ CH ₂ CH ₂ O- ch ₃ ch ₃ OH 2 0 H H -och ₂ ch ₂ ch ₂ o- ch ₃ H OH 2 0 H H -och ₂ ch ₂ ch ₂ o- H H OH 2 0 H H -och ₂ ch ₂ ch ₂ o- Cl Cl OH 2 0 H H -och ₂ ch ₂ ch ₂ o- Cl H OH 2 0 H H -och ₂ ch ₂ ch ₂ o · Cl ch ₃ OH 2 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ OH 2 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ H OH 2 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- H H OH 2 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- Cl Cl OH 2 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o · Cl H OH 2 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- Cl ch ₃ OH 2 0 ch ₃ H -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ OH 2 0 ch ₃ H -och ₂ ch ₂ ch ₂ o- ch ₃ H OH 2 0 ch ₃ H -och ₂ ch ₂ ch ₂ o- H H OH 2 0

ch ₃ H -OCH ₂ CH ₂ CH ₂ O · Cl Cl OH ₂ 0 CH 3 H -och ₂ ch ₂ ch ₂ o- Cl H OH ₂ 0 ch ₃ H -och ₂ ch ₂ ch ₂ o- Cl ch ₃ OH 2 0 H H -och ₂ ch ₂ o- ch ₃ ch ₃ OH ₂ T H H -och ₂ ch ₂ o- ch ₃ H OH 2 ₂ H H -och ₂ ch ₂ o- H H OH 2 ₂ H H -och ₂ ch ₂ o- Cl Cl OH 2 2 H H -OCH ₂ CH ₂ O- Cl H OH 2 2 H H -och ₂ ch ₂ o- Cl ch ₃ OH 2 2 ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ ch ₃ OH ₂ 2 ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ H OH 2 2 ch ₃ ch ₃ -och ₂ ch ₂ o- H H OH 2 2 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl OH 2 0 x ch ₃ ch ₃ -och ₂ ch ₂ o- Cl H OH 2 2 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl ch ₃ OH 2 2 ch ₃ H -och ₂ ch ₂ o- ch ₃ ch ₃ OH 2 2 ch ₃ H -och ₂ ch ₂ o- ch ₃ H OH 2 2 ch ₃ H -och ₂ ch ₂ o- H H OH 2 2 ch ₃ H -och ₂ ch ₂ o- Cl Cl OH 2 2 ch ₃ H -och ₂ ch ₂ o- Cl H OH 2 2 ch ₃ H -och ₂ ch ₂ o- Cl CK ₃ OH 2 2 H H -OCH ₂ CH (CH ₃ ) 0 - ch ₃ ch ₃ OH 2 2 H H -OCH ₂ CH (CH ₃ ) O - ch ₃ H OH 2 2 H H -OCH ₂ CH (CH ₃ ) O - H H OH 2 2 H H -OCH ₂ CH (CH ₃ ) O - Cl Cl OH 2 0 H H -OCH ₂ CH (CH ₃ ) O - Cl H OH 2 2 H H -OCH ₂ CH (CH ₃ ) O - Cl CK ₃ OH 2 2 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ OH 2 2 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - ch ₃ H OH 2 2 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - H H OH 2 2 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - Cl Cl OH 2 2 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - Cl H . OH 2 2 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - Cl CK ₃ OH 2 2 ch ₃ H -OCH ₂ CH (CH ₃ ) O - ch ₃ CH 3 OH 2 0 x ch ₃ H -OCH ₂ CH (CH ₃ ) O - ch ₃ H OH 2 2 ch ₃ H -OCH ₂ CH (CH ₃ ) O - H H OH 2 2 ch ₃ H -OCH ₂ CH (CH ₃ ) O - Cl Cl OH 2 2 ch ₃ H -OCH ₂ CH (CH ₃ ) O - Cl H OH 2 2

63rd

ch ₃ H H H H H H H H H H H CH ₃ OCH (CH ₃₎ O- -OCH ₂ CH ₂ CH ₂ O- -OCH ₂ CH ₂ CH ₂ O · _{-OCH2 CH2 CH2} O- -OCH ₂ CH ₂ CH ₂ ° - OCH ₂ CH ₂ ch ₂ o- H H -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ H -OCH ₂ CH ₂ CH ₂ O · ch ₃ H -och ₂ ch ₂ ch ₂ o- ch ₃ H -och ₂ ch ₂ ch ₂ o- ch ₃ H -och ₂ ch ₂ ch ₂ o- ch ₃ H -och ₂ ch ₂ ch ₂ o- ch ₃ H -och ₂ ch ₂ ch ₂ o- H H -sch ₂ ch ₂ s- H H -sch ₂ ch ₂ s- H H -sch ₂ ch ₂ s- H H -sch ₂ ch ₂ s- H H -sch ₂ ch ₂ s- H H -sch ₂ ch ₂ s- H H -sch ₂ ch ₂ s- H H -sch ₂ ch ₂ s- ch ₃ ch ₃ -sch ₂ ch ₂ s- ch ₃ ch ₃ -sch ₂ ch ₂ s- ch ₃ ch ₃ -sch ₂ ch ₂ s- ch ₃ ch ₃ -sch ₂ ch ₂ s- ch ₃ ch ₃ -sch ₂ ch ₂ s- ch ₃ ch ₃ -sch ₂ ch ₂ s- ch ₃ H -sch ₂ ch ₂ s- ch ₃ H -sch ₂ ch ₂ s- ch ₃ H -sch ₂ ch ₂ s- ch ₃ H -sch ₂ ch ₂ s- ch ₃ H -sch ₂ ch ₂ s-

Cl ch ₃ OH n 0 CH ₃ ch ₃ OH ₂ ch ₃ H OH ₂ 2 H H OH ₂ 2 Cl Cl OH 2 2 Cl H OH 2 2 Cl CH ₃ OH 2 2 ch ₃ OH ₂ 2 ch ₃ H OH 2 2 H H OH 2 2 Cl Cl OH 2 2 Cl H OH 2 2 Cl ch ₃ OH 2 2 ch ₃ ch ₃ OH 2 ₂ ch ₃ H OH 2 ₂ H H OH 2 2 Cl Cl OH 2 2 Cl H OH 2 2 Cl ch ₃ OH 2 2 ch ₃ ch ₃ OH 2 1 ch ₃ ch ₃ OH 0 1 ch ₃ H OH 2 1 H H OH 2 1 Cl Cl OH 2 1 Cl H OH 2 I Cl ch ₃ OH 2 1 no ₂ H OH 2 1 ch ₃ ch ₃ OH 2 1 ch ₃ H OH 2 1 H H OH 2 1 Cl Cl OH 2 1 Cl H OH 2 1 Cl ch ₃ OH 2 1 ch ₃ ch ₃ OH 2 1 ch ₃ H OH 2 1 H H OH 2 1 Cl Cl OH 2 1 Cl H OH ? 1

CH H -sch ₂ ch ₂ s- Cl ch ₃ OH 2 I H H -SCH ₂ CH ₂ O- ch ₃ ch ₃ OH 2 1 H H -SCH ₂ CH ₂ O- ch ₃ ch ₃ OH 0 I H H -sch ₂ ch ₂ o- ch ₃ H OH 2 1 H H -sch ₂ ch ₂ o- H H OH ₂ I H H -sch ₂ ch ₂ o- Cl Cl OH 2 1 H H -sch ₂ ch ₂ o- Cl H OH 2 1 H H -sch ₂ ch ₂ o- Cl CH3 OH 2 1 H H -sch ₂ ch ₂ o- no ₂ H OH 2 1 ch ₃ ch ₃ -SCH ₂ CH ₂ O. ch ₃ CK ₃ OH 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ o · ch ₃ H OH 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ o- H H OH ₂ 1 ch ₃ ch ₃ -sch ₂ ch ₂ o- Cl Cl OH 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ o- Cl H OH 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ o- Cl CH ₃ OH 2 1 ch ₃ H -sch ₂ ch ₂ o- ch ₃ CK ₃ OH 2 1 ch ₃ H -sch ₂ ch ₂ o- ch ₃ H OH 2 1 ch ₃ H -sch ₂ ch ₂ o- H H OH 2 1 ch ₃ H -sch ₂ ch ₂ o- Cl Cl OH 2 1 ch ₃ H -sch ₂ ch ₂ o- Cl H OH 2 1 ch ₃ H -sch ₂ ch ₂ o- Cl CH ₃ OH 2 1 H H -sch ₂ ch ₂ ch ₂ s- ch ₃ ck ₃ OH 2 1 H H -sch ₂ ch ₂ ch ₂ s- ch ₃ H ? H 2 1 H H -sch ₂ ch ₂ ch ₂ s- H H OH 2 1 H H -sch ₂ ch ₂ ch ₂ s- Cl Cl OH 2 1 H H -sch ₂ ch ₂ ch ₂ s- Cl H OH 2 1 H H -sch ₂ ch ₂ ch ₂ s- Cl ch ₃ OH 2 1 H H -sch ₂ ch ₂ ch ₂ s- no ₂ H OH 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- ch ₃ ch ₃ OH 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- ch ₃ H OH 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- H H OH '2 1 ch ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- Cl Cl OH 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- Cl H OH 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- Cl ch ₃ OH 2 1 ch ₃ H -sch ₂ ch ₂ ch ₂ s- ch ₃ CK ₃ OH .2 1 ch ₃ H -sch ₂ ch ₂ ch ₂ s- ch ₃ H OH 2 1 ch ₃ H -sch ₂ ch ₂ ch ₂ s- H H OH 2 1 ch ₃ H -sch ₂ ch ₂ ch ₂ s- Cl Cl OH 2 -1

ch ₃ H -SCH ₂ CH ₂ CH ₂ · Cl H OH ₂ ch ₃ H -sch ₂ ch ₂ ch ₂ s- Cl ch ₃ OH ₂ H H 0X0 ch ₃ ch ₃ OH 2 H H 0X0 ch ₃ H OH 2 H H 0X0 H H OH ₂ H H 0X0 Cl Cl OH 2 H H 0X0 Cl H OH 2 H H 0X0 Cl CH ₃ OH 2 H H 0X0 no ₂ H OH 2 ch ₃ ch ₃ 0X0 ch ₃ ch ₃ OH 2 ch ₃ ch ₃ 0X0 ch ₃ H OH 2 ch ₃ ch ₃ 0X0 H H OH 2 ch ₃ ch ₃ 0X0 Cl Cl OH 2 ch ₃ CH ₃ 0X0 Cl H OH 2 ch ₃ ch ₃ 0X0 Cl CH ₃ OH 2 ch ₃ H 0X0 ch ₃ ch ₃ OH 2 ch ₃ H 0X0 ch ₃ H OH 2

ch ₃ H 0X0 H H OH 2 ch ₃ H 0X0 Cl Cl OH 2 ch ₃ H 0X0 Cl H OH 2 ch ₃ H 0X0 Cl ch ₃ OH 2 H H 0X0 ch ₃ ch ₃ OH 1 H H 0X0 ch ₃ H OH 1 H H 0X0 H H OH 1 H H 0X0 Cl Cl OH 1 H H 0X0 Cl H OH 1 H H 0X0 Cl ch ₃ OH 1 ch ₃ ch ₃ 0X0 ch ₃ ch ₃ OH 1 ch ₃ ch ₃ 0X0 ch ₃ H OH 1 ch ₃ ch ₃ 0X0 H H OH ] ch ₃ ch ₃ 0X0 ci Cl OH 1 ch ₃ ch ₃ 0X0 Cl H OH 1 ch ₃ ch ₃ 0X0 Cl ch ₃ OH 1 ch ₃ H 0X0 ch ₃ CH 3 OH ] ch ₃ H 0X0 ch ₃ H OH 1 ch ₃ H 0X0 H H OH 1 ch ₃ H 0X0 Cl Cl OH 1 ch ₃ H 0X0 Cl H OH 1

CHi

0X0

Cl

CH ₃ OH 1

Table 2

R 1 R ² F ⁴ Q

N - CH ₂ CH ₃

_R 3a _R 3b R ¹ R ² R ⁴ R ⁵ n m H H -OCH ₂ CH ₂ O- ch ₃ ch ₃ 2 1 H H -och ₂ ch ₂ o- ch ₃ H 2 1 H H -och ₂ ch ₂ o- H H 2 1  H H -och ₂ ch ₂ o- Cl Cl 2 1 H H -och ₂ ch ₂ o- Cl H 2 1 H H -och ₂ ch ₂ o- Cl ch ₃ 2 ] H H -och ₂ ch ₂ o- no ₂ H 2 1 ch ₃ CH 3 -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ ch ₃ -och ₂ ch ₂ o- H H 2 ] ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl 2 1 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl H 2 1 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl ch _{3 2} 1 ch ₃ H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ H -och ₂ ch ₂ o- ch ₃ H 2 ] CH 2 H -och ₂ ch ₂ o- H H 2 1 ch ₃ H -och ₂ ch ₂ o- Cl Cl 2 1 ch ₃ H -och ₂ ch ₂ o- Cl H 2 1 ch ₃ H -och ₂ ch ₂ o- Cl ch ₃ 2 1 H H -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ 2 1 H H -OCH ₂ CH (CH ₃ ) O - ch ₃ H 2 1 H H -OCH ₂ CH (CH ₃ ) O - H H 2  1 H H -OCH ₂ CH (CH ₃ ) O - Cl Cl 2 1 H H -OCH ₂ CH (CH ₃ ) O - Cl H 2 First H H -OCH ₂ CH (CH ₃ ) O - Cl ch ₃ 2 1 ch ₃ CH ₃ -OCH ₂ CH (CH ₃ ) 0 - ch ₃ ch ₃ 2 1 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - ch ₃ H 2 1 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - H H 2 1

CH ;, ch ₃ -OCH ₂ CHCH ₃ ) O- Cl Cl ₂ 1 CH ;, CH ;, -OCH ₂ CH (CH ₃ ) O - Cl H ₂ 1 CH ;, ch ₃ -OCH ₂ CH (CH ₃ ) O - Cl CH ;, ₂ 1 CH ;, H -OCH ₂ CH (CH ₃ ) O - ch ₃ ch _{3 2} 1 CH; H -OCH ₂ CH (CH ₃ ) O - ch ₃ H 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) O - H H 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) O - Cl Cl 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) O - Cl H 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) O - Cl ch ₃ 2 1 H H -OCH ₂ CH ₂ CH ₂ O- ch ₃ ch ₃ 2 1 H H -och ₂ ch ₂ ch ₂ o- ch ₃ H 2 1 H H -och ₂ ch ₂ ch ₂ o- H H 2 1 H H -och ₂ ch ₂ ch ₂ o- Cl Cl 2 ] H H -och ₂ ch ₂ ch ₂ o- Cl H 2 1 H H -och ₂ ch ₂ ch ₂ o- Cl ch ₃ 2 ] ch ₃ CH ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- H H 2 1 CH ₃ CH ;, -och ₂ ch ₂ ch ₂ o- Cl Cl 2 1 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- Cl H 2 1 CH v ch ₃ -och ₂ ch ₂ ch ₂ o- Cl ch ₃ 2 1 ch ₃ H -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ H -och ₂ ch ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ H -och ₂ ch ₂ ch ₂ o- H H 2 1 ch ₃ H -och ₂ ch ₂ ch ₂ o- Cl Cl 2 1 ch ₃ H -och ₂ ch ₂ ch ₂ o- Cl H 2 1 ch ₃ H -och ₂ ch ₂ ch ₂ o- Cl ch ₃ 2 1 H H ch ₃ o ch ₃ o ch ₃ ch ₃ 2 1 H H ch ₃ o ch ₃ o ch ₃ H 2 1 H H ch ₃ o ch ₃ o Cl Cl 2 1 H H ch ₃ o ch ₃ o Cl H 2 1 H H ch ₃ o ch ₃ o Cl ch ₃ 2 1 ch ₃ ch ₃ CH 2 O CH ₃ O ch ₃ ch ₃ 2 1 ch ₃ CH 3 ch ₃ o ch ₃ o ch ₃ H 2 1 ch ₃ ch ₃ ch ₃ o ch ₃ o H H 2 1 ch ₃ ch ₃ ch ₃ o ch ₃ o Cl Cl 2 1 ch ₃ ch ₃ ch ₃ o ch ₃ o Cl H 2 1 ch ₃ ch ₃ ch ₃ o ch ₃ o Cl ch ₃ 2 1

ch ₃ H ch ₃ o ch ₃ o CH3 ch ₃ 2 I ch ₃ H ch ₃ o ch ₃ o ch ₃ H 2 1 ch ₃ H CH ₃ O ch ₃ o H H 2 1 ch ₃ H CH ₃ O ch ₃ o Cl Cl 2 1 ch ₃ H CH3O ch ₃ o Cl H 2 1 ch ₃ H ch ₃ o ch ₃ o Cl ch ₃ 2 1 H H h ₅ c ₂ o h ₅ c ₂ o ch ₃ ch ₃ 2 1 H H h ₅ c ₂ o h ₅ c ₂ o ch ₃ H 2 1 H H h ₅ c ₂ o h ₃ c ₂ o H H 2 1 H H h ₅ c ₂ o h ₅ c ₂ o Cl Cl 2 1 H H h ₅ c ₂ o h ₅ c ₂ o Cl H 2 1 H H h ₅ c ₂ o h ₅ c ₂ o Cl ch ₃ 2 1 ch ₃ ch ₃ h ₅ c ₂ 0 h ₅ c ₂ o ch ₃ ch ₃ 2 1 ch ₃ ch ₃ h ₅ c ₂ o h ₅ c ₂ o ch ₃ H 2 1 ch ₃ ch ₃ h ₅ c ₂ o h ₅ c ₂ o H H 2 1 ch ₃ ch ₃ h ₅ c ₂ o h ₅ c ₂ o Cl Cl 2 1 ch ₃ ch ₃ h ₅ c ₂ o h ₅ c ₂ o Cl H 2 1 ch ₃ ch ₃ h ₅ c ₂ o h ₅ c ₂ o Cl ch ₃ 2 1 ch ₃ H H ₅ C ₂ O h ₅ c ₂ o ch ₃ ch ₃ 2 1 ch ₃ H h ₅ c ₂ o h ₅ č ₂ 0 ch ₃ H 2 ] ch ₃ H h ₅ c ₂ o h ₅ c ₂ o H H 2 1 ch ₃ H h ₅ c ₂ o h ₅ c ₂ o Cl Cl 2 1 ch ₃ H h ₅ c ₂ o h ₅ c ₂ o Cl H n 1 ch ₃ H h ₅ c ₂ o h ₅ c ₂ o Cl ch ₃ 2 ] H H -och ₂ ch ₂ o- ch ₃ ch ₃ 0 1 H H -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ 0 1 H H -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ 0 1 H H ch ₃ o ch ₃ o ch ₃ ch ₃ 0 1 H H h ₃ c ₂ o h ₅ c ₂ o ch ₃ ch ₃ 0 1 H H -och ₂ ch ₂ o- ch ₃ ch ₃ 1 1 H H -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ 1 1 H H -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ 1 '] H H ch ₃ o ch ₃ o ch ₃ ch ₃ 1 1 H H h ₅ c ₂ o h ₅ c ₂ o ch ₃ ch ₃ 1 • 1 H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 2 H H -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ 2 2 H H -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ 2 2 H H ch ₃ o ch ₃ o ch ₃ ch ₃ 2 2

Η Η Η Η Η Η H H H . H H H C ₂ H ₅ OH C ₂ H ₅ CH ₂ CH ₂ CH ₂ CH 2 CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ · CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ch ₂ ch ₂ - ch ₃ · ch ₃ ch ₃ H Cl Cl ch ₃ ch ₃ H H Cl H n ₂ 2 2 _{2 2} 2 1 l 1 1 1 Η H -ch ₂ ch ₂ ch ₂ ch ₂ - Cl ch ₃ 2 l ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ ch _{3 2} 1 · CH. . ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ - CH ₃ H 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ - H H ₂ 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ - Cl Cl 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ - Cl H ₂ 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ - Cl ch _{3 2} 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ CH3 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ H ₂ 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ · H H 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ - Cl Cl 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ - Cl H 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ - Cl ch _{3 2} 1 H H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ ch ₃ 2 1 H H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ H 2 ] H H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - H H 2 1 H H -CH ₂ CH-> CH ₂ CH ₂ CH ₂ - Cl Cl ₂ 1 H H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - Cl H 2 1 H H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - Cl ch ₃ 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ ch ₃ 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ H 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - H H 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - Cl Cl 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - Cl H 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - Cl ch ₃ 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - ch ₃ ch ₃ 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ · ch ₃ H ₂ 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - H H 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - Cl Cl 2 ] ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - Cl H 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ ch ₂ ch ₂ - Cl ch ₃ 2 1 H H -ch ₂ ch ₂ ch ₂ o- ch ₃ CH 3 2 1

Η H -CH ₂ CH ₂ CH ₂ O- ch ₃ H 2 1 Η H -ch ₂ ch ₂ ch ₂ o- H H ₂ 1 Η H -ch ₂ ch ₂ ch ₂ o · Cl Cl ₂ 1 Η H -ch ₂ ch ₂ ch ₂ o- Cl H ₂ 1 Η H -ch ₂ ch ₂ ch ₂ o- Cl ch ₃ 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o · ch ₃ ch _{3 2} 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- ch ₃ H ₂ 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- H H 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- Cl Cl ₂ 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ Cl H 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- Cl ch ₃ 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ o- CH ₃ ch ₃ 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ o · H H ₂ 1 ch ₃ H -ch ₂ ch ₂ ch ₂ o- Cl Cl ₂ 1 ch ₃ H -ch ₂ ch ₂ ch ₂ o- Cl H ₂ 1 ch ₃ H -ch ₂ ch ₂ ch ₂ o- Cl ch _{3 2} 1 H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 0 H H -och ₂ ch ₂ o- ch ₃ H ₂ 0 H H -och ₂ ch ₂ o- H H ₂ 0th H H -qch ₂ ch ₂ o- Cl Cl ₂ 0 H H -och ₂ ch ₂ o- Cl H n 0 H H -qch ₂ ch ₂ o- Cl ch _{3 2} 0 ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ ch _{3 2} 0 ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ H 2 0 ch ₃ ch ₃ -och ₂ ch ₂ o- H H ₂ 0 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl 2 0 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl H 2 0 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl ch ₃ 2 0th ch ₃ H -OCH ₂ CH ₂ O- ch ₃ ch _{3 2} 0 ch ₃ H -och ₂ ch ₂ o- ch ₃ H 2 0 ch ₃ H -OCH ₂ CH ₂ O- H H 2 0 ch ₃ H -qch ₂ ch ₂ o-. Cl Cl T 0 ch ₃ H -OCH ₂ CH ₂ 0- Cl H ₂ 0 ch ₃ H -och ₂ ch ₂ o- Cl ch ₃ 2 0 H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 2 H H -qch ₂ ch ₂ o- ch ₃ H 2 2 H H -och ₂ ch ₂ o- H H 2 2

Η H -OCH ₂ CH ₂ O- Cl ci 2 2 Η H -och ₂ ch ₂ o- Cl H 2 ₂ Η H -och ₂ ch ₂ o- Cl ch ₃ 2 n ch ₅ ch ₃ -och ₂ ch ₂ o- ch ₃ ch _{3 2 2} ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ H 2 2 ch ₃ ch ₃ -och ₂ ch ₂ o- H H 2 2 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl 2 2 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl H 2 ₂ ch ₃ ch ₃ -och ₂ ch ₂ o- Cl ch ₃ 2 ₂ ch ₃ H -och ₂ ch ₂ o- ch ₃ ch _{3 2} 2 ch ₃ H -och ₂ ch ₂ o- ch ₃ H 2 2 ch ₃ H -och ₂ ch ₂ o- H H ₂ 2 ch ₃ H -och ₂ ch ₂ o- Cl Cl ₂ 2 ch ₃ H -o-ch ₂ ch ₂ -o- Cl H <5 2 ch ₃ H _{-O-CH2 CH2} -O- Cl ch _{3 2} 2 H H -och ₂ ch ₂ ch ₂ ch ₃ ch _{3 2} 0 H H -och ₂ ch ₂ ch ₂ ch ₃ H 2 0 H H -och ₂ ch ₂ ch ₂ H H 2 0 H H -och ₂ ch ₂ ch ₂ Cl Cl 2 0 H H -och ₂ ch ₂ ch ₂ Cl H 2 0 H H -och ₂ ch ₂ ch ₂ Cl ch ₃ 2 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ CH3 ch ₃ 2 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ ch ₃ H 2 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ H H 2 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ Cl Cl 2 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ Cl H 2 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ Cl ch ₃ 2 0 ch ₃ H -och ₂ ch ₂ ch ₂ ch ₃ ch ₃ 2 0 ch ₃ H -och ₂ ch ₂ ch ₂ ch ₃ H 2 0 ch ₃ H -och ₂ ch ₂ ch ₂ H H 2 0 ch ₃ H -och ₂ ch ₂ ch ₂ Cl Cl 2 0 ch ₃ H -och ₂ ch ₂ ch ₂ Cl H 2 0 ch ₃ H -och ₂ ch ₂ ch ₂ Cl ch ₃ 2 0 H H -sch ₂ ch ₂ s- ch ₃ ch ₃ 2 1 H H -sch ₂ ch ₂ s- ch ₃ ch ₃ 0 1 H H -sch ₂ ch ₂ s- ch ₃ H 2 1 H H -sch ₂ ch ₂ s- H H 2 1 H H -sch ₂ ch ₂ s- Cl Cl 2 1

Η H -sch ₂ ch ₂ s- Cl H 2 I Η H -sch ₂ ch ₂ s- Cl ch ₃ 2 1 Η H -sch ₂ ch ₂ s- no ₂ H 2 1 ch ₃ CH ₃ -sch ₂ ch ₂ s- ch ₃ ch ₃ 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ s- ch ₃ H 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ s- H H 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ s- Cl Cl 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ s- Cl H 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ s- Cl ch ₃ 2 ] ch ₃ H -sch ₂ ch ₂ s- CH ₃ ch ₃ 2 1 ch ₃ H -sch ₂ ch ₂ s- ch ₃ H 2 1 ch ₃ H -sch ₂ ch ₂ s- H H 2 1 ch ₃ H -sch ₂ ch ₂ s- Cl Cl 2 1 ch ₃ H -sch ₂ ch ₂ s- Cl H 2 1 ch ₃ H -sch ₂ ch ₂ s- Cl ch ₃ 2 1 H H -sch ₂ ch ₂ o- ch ₃ ch ₃ 2 1 H H -sch ₂ ch ₂ o- ch ₃ ch ₃ 0 1 H H -sch ₂ ch ₂ o- ch ₃ H 2 1 H H -sch ₂ ch ₂ o- H H 2 1 H H -sch ₂ ch ₂ o- Cl Cl 2 1 H H • sch ₂ ch ₂ o- Cl H 2 1 H H -sch ₂ ch ₂ o- Cl ch ₃ 2 1 H H -sch ₂ ch ₂ o- no ₂ H 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ o- H H 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ o- Cl Cl 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ o- Cl H 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ o- Cl CH ₃ 2 1 ch ₃ H ' -sch ₂ ch ₂ o- CH3 ch ₃ 2 1 ch ₃ H -sch ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ H -sch ₂ ch ₂ o- H H 2 1 ch ₃ H -sch ₂ ch ₂ o- Cl Cl 2 1 H -sch ₂ ch ₂ o- Cl H 2 1 ch ₃ H -sch ₂ ch ₂ o- Cl ch ₃ 2 1 H H -sch ₂ ch ₂ ch ₂ s- ch ₃ ch ₃ 2 j H H -sch ₂ ch ₂ ch ₂ s- ch ₃ H ₂ 1 H H -sch ₂ ch ₂ ch ₂ s- H H ₂ 1

Η H -sch ₂ ch ₂ ch ₂ s- Cl Cl ₂ l Η H -sch ₂ ch ₂ ch ₂ s- Cl H ₂ I Η H -sch ₂ ch ₂ ch ₂ s- Cl ch ₃ 2 1 Η H -sch ₂ ch ₂ ch ₂ s- K0 ₂ H 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- ch ₃ ch ₃ 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- ch ₃ H 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- H H 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- Cl Cl 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- Cl H 2 1 ch ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- Cl ch ₃ 2 1 ch ₃ H -sch ₂ ch ₂ ch ₂ s- ch ₃ ch ₃ 2 1 ch ₃ H -sch ₂ ch ₂ ch ₂ s- ch ₃ H 2 1 ch ₃ H -sch ₂ ch ₂ ch ₂ s- H H 2 I ch ₃ H -sch ₂ ch ₂ ch ₂ s- Cl Cl 2 1 ch ₃ H -sch ₂ ch ₂ .ch ₂ s- Cl H 2 1 ch ₃ H -sch ₂ ch ₂ ch ₂ s- Cl ch ₃ 2 1 H H 0X0 ch ₃ ch ₃ 2 1 H H 0X0 ch ₃ H 2 1 H H 0X0 Cl Cl 2 1 H H 0X0 Cl H 2 1 H H 0X0 Cl ch ₃ 2 ] H H 0X0 no ₂ H 2 1 ch ₃ ch ₃ 0X0 ch ₃ ch ₃ 2 ] ch ₃ ch ₃ 0X0 ch ₃ H 2 1 ch ₃ ch ₃ 0X0 H H 2 1 ch ₃ ch ₃ 0X0 Cl Cl 2 1 ch ₃ ch ₃ 0X0 Cl H 2 1 ch ₃ ch ₃ 0X0 Cl ch ₃ 2 1 ch ₃ H 0X0 ch ₃ ch ₃ 2 1 ch ₃ H 0X0 ch ₃ H 2 1 ch ₃ H 0X0 H H 2 1 ch ₃ H 0X0 Cl Cl 2 1 ch ₃ H 0X0 Cl H 2 1 ch ₃ H 0X0 Cl ch ₃ 2 1 H H 0X0 ch ₃ CHI 1 1 H H 0X0 ch ₃ H 1 1 H H 0X0 H H 1 1 H H 0X0 Cl Cl 1 1

H H 0X0 Cl H 1 1 H H 0X0 Cl CH; 1 I CH; ch ₃ 0X0 ch ₃ CH; 1 1 CH; ch ₃ 0X0 ch ₃ H 1 1 CH; CH; 0X0 H H 1 1 CH; CH; 0X0 Cl Cl 1 1 CH; ch ₃ 0X0 Cl H 1 1 CH; CH; 0X0 Cl CH; 1 1 CH; H 0X0 CH; CH; 1 1 CH; H 0X0 CH; H 1 1 CH; H 0X0 H H 1 1 CH; H 0X0 Cl Cl 1 1 ch ₃ H 0X0 Cl H 1 1 CH; H 0X0 Cl CH; 1 1

Table 3

R ^3a R ^3b HHHHHHHHHHHHHHHHHHHHH

Λη

R ^3a - R ^{3b /} R ¹ R ² (0) n R ⁴ in R ⁵ R5 N — R ⁹ ./V R 10 ⁷ R ⁸ R ⁹ -OCH ₂ CH ₂ O- CH; CH; SO ₂ CH; ^C 2 ^H 5 -och ₂ ch ₂ o- ch ₃ CH; with ₂ ch ₂ ci c ₂ h ₅ -och ₂ ch ₂ o- CH; H SO ₂ CH; c ₂ h ₅ -och ₂ ch ₂ o- H H Sat ₂ ch ₃ c ₂ h ₅ -och ₂ ch ₂ o- Cl Cl SO ₂ CH; c ₂ h ₅ -och ₂ ch ₂ o- Cl H SO ₂ CH; C ₂ H; -och ₂ ch ₂ o- Cl CH; SO ₂ CH; c ₂ h ₅ -och ₂ ch ₂ o- CH; CH; Sat ₂ c ₂ h ₅ ^C 2 ^H 5 -och ₂ ch ₂ o- CH; H S ° ₂ C ₂ H; c ₂ h ₅ -och ₂ ch ₂ o- H H Sat ₂ c ₂ h ₅ c ₂ h ₅ -och ₂ ch ₂ o- Cl Cl Sat ₂ c ₂ h ₅ c ₂ h ₅ -och ₂ ch ₂ o- Cl H Sat ₂ c ₂ h ₃ c ₂ h ₅ -och ₂ ch ₂ o- Cl CH; Sat ₂ c ₂ h ₅ c ₂ h ₅ -och ₂ ch ₂ o- CH; CH; SO ₂ -nC; Hy c ₂ h ₅ -och ₂ ch ₂ o- ch ₃ H SO ₂ - / C, H 7 c ₂ h ₅

RLO

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

Η Η Η Η Η Η Η Η Η Η Η H Η Η -och ₂ ch ₂ o -och ₂ ch ₂ o -och ₂ ch ₂ o -och ₂ ch ₂ o -och ₂ ch ₂ o -och ₂ ch ₂ o -och ₂ ch ₂ o- H Cl Cl Cl ch ₃ ch ₃ H H Cl H _{CH3 CH3} H H SO ₂ -rt-C ₃ H ₂ SO-tC ₃ H 7 SO 1 - - C ₃ H ₃ SO ₃ / C ₃ H ₂ SO ₂ -nC ₄ H ₃ SO ₃ -nC ₄ Hg C ₂ H ₅ C ₂ H ₅ ^C 2 ^H 5 C ₂ H ₅ C ₂ H ₃ C ₂ H ₅ C ₂ H ₅ H H H H H H H 2 2 2 Ό 2 2 2 1 1 1 1 1 1 1 Η Η -och ₂ ch ₂ o- Cl Cl Sol-N-C ^ Hg c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- Cl H Soo-N-C ^ Hg C ₂ H ₅ H 2 1 Η Η -och ₂ ch ₂ o- Cl ch ₃ SO ₂ - / iC ₄ Hg c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ -p-tolyl c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- ch ₃ H SO ₂ -p-tolyl c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- H H SO ₂ -p-tolyl c ₂ h ₅ H 2 I Η Η -och ₂ ch ₂ o- Cl Cl SO ₂ -p-tolyl c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- Cl H SO ₂ -p-tolyl c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- Cl ch ₃ Sol-p-tolyl c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ -p-NO ₂ C ₆ H ₄ c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- CH ₃ H SO ₂ -p-NO ₂ C ₆ H ₄ c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- H H Sat ₂ -p-no ₂ c ₆ h ₄ c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- Cl Cl SO ₂ -p-NO ₂ C ₆ H ₄ c ₂ h ₅ H 2 1 H Η -och ₂ ch ₂ o- Cl H SO ₂ -p-NO ₂ C ₆ H ₄ c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- Cl ch ₃ SO ₂ -p-NO ₂ C ₆ H ₄ c ₂ h ₅ H 2 1 Η Η -och ₃ ch ₂ o- ch ₃ CH ₃ SO ₂ -p-C1C ₆ H ₄ - c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- ch ₃ H SO ₂ -p-CIC ₆ H ₄ c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- H H SO ₂ -p-ClC ₆ H ₄ c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- Cl Cl SO ₂ -p-CIC ₆ H ₄ c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- Cl H Sat ₂ -p-cic ₆ h ₄ c ₂ h ₅ H 2 ] Η Η -och ₂ ch ₂ o- Cl CH ₃ SO ₂ -p-CIC ₆ H ₄ c ₂ h ₅ H 2 . ] Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ C (= O) _CH3 c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- ch ₃ H C (= O) _CH3 c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- H H C (= O) _CH3 c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- Cl Cl C (= O) _CH3 c ₂ h ₃ H 2 ] Η Η -och ₂ ch ₂ o- Cl H Ci = O) _CH3 c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- Cl CH ₃ C (= O) _CH3 c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ C (= O) C ₂ H ₅ c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- ch ₃ H C (= O) C ₂ H ₅ c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- H H C (= O) C ₂ H ₅ c ₂ h ₅ H 2 1 Η Η -och ₂ ch ₂ o- Cl Cl C (= O) C ₂ H ₅ c ₂ h ₅ H 2 1

ΊΑ

Η Η -och ₂ ch ₂ o · Cl H C (= O) C ₂ H ₅ c ₂ h ₅ H n 1 Η Η -och ₂ ch ₂ o- Cl CH ₃ C (= O) C ₂ H ₅ c ₂ h ₅ H ₂ F Η Η -och ₂ ch ₂ o- ch ₃ CH with ₂ ch ₂ ci ch ₃ H 2 1 Η Η -och ₂ ch ₂ o- ch ₃ H with ₂ ch ₂ ci ch ₃ H ₂ and Η Η -och ₂ ch ₂ o- H H with ₂ ch ₂ ci ch ₃ H 2 1 Η Η -och ₂ ch ₂ o- Cl Cl with ₂ ch ₂ ci ch ₃ H 2 1 Η Η -och ₂ ch ₂ o- Cl H with ₂ ch ₂ ci ch ₃ H 2 1 Η Κ -och ₂ ch ₂ o- Cl ch ₃ with ₂ ch ₂ ci ch ₃ H 2 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ -nC ₃ Hj ch ₃ H ₂ 1 Η Η -och ₂ ch ₂ o- ch ₃ H SO ₂ -nC ₃ H ₇ ch ₃ H 2 1 Η Η -och ₂ ch ₂ o- H H SO ₂ -nC ₃ H ₇ ch ₃ H 2 1 Η Η -och ₂ ch ₂ o- Cl Cl SO ₂ -nC ₃ H ₇ ch ₃ H 2 1 Η Η -och ₂ ch ₂ o- Cl H SO ₂ -nC ₃ K ₇ ch ₃ H 2 1 Η Η -och ₂ ch ₂ o- Cl ch ₃ SO ₂ .nC ₃ H ₇ ch ₃ H 2 j Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ -p-tolyl ch ₃ H 2 1 Η Η -och ₂ ch ₂ o- ch ₃ H SO ₂ -p-to1vl ch ₃ H ₂ 1 Η Η -och ₂ ch ₂ o- H H SO ₂ -p-tolyl ch ₃ H 2 1 Η Η -och ₂ ch ₂ o- Cl Cl SO ₂ -p-tolyl ch ₃ H 2 1 Η Η -och ₂ ch ₂ o- Cl H SO ₂ -p-iolyl ch ₃ H 2 1 Η Η -och ₂ ch ₂ o- Cl ch ₃ SO ₂ -p-iolyl ch ₃ H 2 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ CH ₃ c ₂ h ₃ H 0 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ Sat ₂ c ₂ h ₅ c ₂ h ₅ H 0 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ -nC ₃ H ₇ c ₂ h ₅ H 0 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ -Zi-C ₄ H9 c ₂ h ₅ H 0 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ -p-tolyl c ₂ h ₅ H 0 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO _{2 -} NO ₂ C ₆ H ₄ c ₂ h ₅ H • 0 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ -p-CIC ₆ K ₄ c ₂ h ₅ H 0 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ C (= O) _CH3 c ₂ h ₅ H 0 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ C (= O) C ₂ H ₅ c ₂ h ₅ H 0 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ Sat ₂ ch ₃ c ₂ h ₅ H 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ ^SO 2 ^c 2 ^h 5 c ₂ h ₅ -H 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ -nC ₃ K ₇ c ₂ h ₅ H 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ -nC ₄ H9 c ₂ h ₅ H 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ -p-tolyl c ₂ h ₃ H 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ .p.NO ₂ C ₆ H ₄ c ₂ h ₅ H 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ -p-CIC ₆ K ₄ c ₂ h ₃ •? .H 1 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ C (= O) _CH3 c ₂ h ₅ Ή 1 Η Η -OCH ₂ CH ₂ O- . CH ₃ ch ₃ C (= O) C ₂ H ₅ c ₂ h ₅ H 1

Η Η -OChhCHnO- ch ₃ ch ₃ Sat ₂ ch ₃ C ₂ ^h 5 H 2 *) Η Η -OCH ₂ CH ₂ 0 · CH ₃ ch ₃ S02C0H5 c ₂ h ₅ H 2 Λ Η Η -och ₂ ch ₂ o- ch ₃ CH 3 SC> 2 - / - - C ₃ H7 c ₂ h ₅ H n 2 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ Sol-N-C ^ Hg c ₂ h ₅ H 2 2 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ -p-tolyl ^c 2 ^h 5 H 2 Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ -p-NO ₂ C ₆ H ₄ c ₂ h ₅ H 2 n Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ SO ₂ -p-CIC ₆ H ₄ c ₂ h ₅ H 2 *) Η Η -och ₂ ch ₂ o- ch ₃ ch ₃ C (= O) _CH3 c ₂ h ₅ H 2 2 Η Η -OCH ₂ CH ₂ O- • ch ₃ ch ₃ C (= O) C ₂ H ₅ C ₂ H ₅ H 2 n

H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ H H H -och ₂ ch ₂ o- CH 3 H 2 1 ch ₃ H H H -och ₂ ch ₂ o- H H 2 1 ^CH 3 H H H -och ₂ ch ₂ o- Cl Cl 2 1 ch ₃ H H H -och ₂ ch ₂ o- Cl H 2 1 ch ₃ H H H -och ₂ ch ₂ o- Cl ch ₃ 2 1 ch ₃ H ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ H ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ H ch ₃ ch ₃ -OCH ₂ CH ₂ O- H H 2 1 ch ₃ H ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl 2 1 ch ₃ H ch ₃ ch ₃ -och ₂ ch ₂ o- Cl H 2 1 ch ₃ H ch ₃ ch ₃ -och ₂ ch ₂ o- Cl ch ₃ 2 1 ch ₃ H ch ₃ H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ H ch ₃ H -och ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ H ch ₃ H -och ₂ ch ₂ o- h H 2 1 ch ₃ H ch ₃ H -och ₂ ch ₂ o- Cl Cl 2 1 ch ₃ H ch ₃ H -och ₂ ch ₂ o- Cl H 2 1 ch ₃ H ch ₃ H -och ₂ ch ₂ o- Cl ch ₃ 2 1 ch ₃ H H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ CH H H -och ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ CH

Η Η Η Η H H H H -och ₂ ch ₂ o -och ₂ ch ₂ o -och ₂ ch ₂ o -och ₂ ch ₂ o- H Cl Cl Cl H Cl H CH; 2 2. ₂ 2 1 1 1 1 CH ₃ CH ₃ CH ch ₃ CH; CH; CH; CH; CH; CH; -och ₂ ch ₂ o- CH; 0 3 * ₂ 1 CH; CH; CH; CH; -och ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ CH; ch ₃ CH; -och ₂ ch ₂ o- H H 2 and ch ₃ CH; ch ₃ CH; -och ₂ ch ₂ o- Cl Cl 2 1 CH ₃ CH; ch ₃ CH; -och ₂ ch ₂ o- Cl H 2 1 ch ₃ CH; ch ₃ CH; -och ₂ ch ₂ o- Cl ch _{3 2} 1 ch ₃ ^CK ; ch ₃ H -och ₂ ch ₂ o- CH; ch ₃ 2 1 ch ₃ CH; ch ₃ H -och ₂ ch ₂ o- CH; H ₂ 1 ch ₃ CH; ch ₃ H -och ₂ ch ₂ o- H H 2 1 ch ₃ CH; CH; H -och ₂ ch ₂ o- Cl Cl 2 1 ch ₃ CH; CH; H -och ₂ ch ₂ o- Cl H 2 1 ch ₃ CH; CH; H -och ₂ ch ₂ o- Cl ch ₃ 2 1 ch ₃ CH; H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 c ₂ h ₅ CH; H H -och ₂ ch ₂ o- CH; H 2 1 C ₂ «5 CH; H H -och ₂ ch ₂ o- H H 2 1 c ₂ h ₅ CH; H H -och ₂ ch ₂ o- Cl Cl 2 1 c ₂ h ₅ CH; H H -och ₂ ch ₂ o- Cl H 2 1 c ₂ h ₅ CH; H H -och ₂ ch ₂ o- Cl ch ₃ 2 1 c ₂ h ₅ CH; CH; CH; -och ₂ ch ₂ o- CH; ch ₃ 2 1 c ₂ h ₅ CH; CH ₃ ch ₃ -och ₂ ch ₂ o- CH; H 2 1 c ₂ h ₅ CH; ch ₃ CH; -och ₂ ch ₂ o- H H 2 1 c ₂ h ₅ CH; ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl 2 1 c ₂ h ₅ CH; ch ₃ CH; -och ₂ ch ₂ o- Cl H 2 1 c ₂ h ₅ CH; H H -och ₂ ch ₂ o- CH; ch ₃ 2 1 Ch ₃ OCH H H -och ₂ ch ₂ o- CH; H 2 I ch ₃ OCH H H -och ₂ ch ₂ o- H H 2 1 CH; OCH H H -och ₂ ch ₂ o- Cl Cl 2 1 CH; OCH H H -och ₂ ch ₂ o- Cl H ₂ 1 ch ₃ 'OCH H H -och ₂ ch ₂ o- Cl ch _{3 2} I ch ₃ OCH CH ₃ CH; -och ₂ ch ₂ o- CH; ch ₃ 2 1 ch ₃ OCH CH; CH; -och ₂ ch ₂ o- CH; H 2 1 ch ₃ ’OCH CH ₃ ch ₃ -och ₂ ch ₂ o- H H 2 1 ch ₃ OCH CH; ch ₃ -och ₂ ch ₂ o- Cl Cl 2 1 CH; OCH CH; ch ₃ -och ₂ ch ₂ o- Cl H 2 1 ch ₃ OCH

CH j CH ₃ -OCH ₂ CH ₂ O- Cl ch ₃ 2 CH 3 OCH; CH ₃ H -OCH ₂ CH ₂ O- ch ₃ ch ₃ 2 ch ₃ OCH 3 ch ₃ H -och ₂ ch ₂ o- ch ₃ H ₂ ch ₃ OCH; ch ₃ ’H -och ₂ ch ₂ o- H H 2 ch ₃ OCH; ch ₃ H -och ₂ ch ₂ o- Cl Cl ₂ ch ₃ OCH; ch ₃ H -och ₂ ch ₂ o- Cl H 2 ch ₃ OCH; ch ₃ H -och ₂ ch ₂ o- Cl CH ₃ 2 ch ₃ OCH; H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 C ₂ H ₅ OCH; H H -och ₂ ch ₂ o- ch ₃ H 2 c ₂ h ₅ OCH; H H -och ₂ ch ₂ o- H H 2 c ₂ h ₅ OCH; H H -och ₂ ch ₂ o- Cl Cl 2 c ₂ h ₅ OCH; H H -och ₂ ch ₂ o- Cl H 2 c ₂ h ₅ OCH; H H -och ₂ ch ₂ o- Cl ch ₃ 2 c ₂ h ₅ OCH; ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ ch ₃ 2 c ₂ h ₅ OCH; ch ₃ ch ₅ -och ₂ ch ₂ o- ch ₃ H 2 C ₂ »5 OCH; ch ₃ ch ₃ -och ₂ ch ₂ o- H H 2 c ₂ h ₅ OCH; ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl 2 c ₂ h ₅ OCH; ch ₃ ch ₃ -och ₂ ch ₂ o- Cl H 2 c ₂ h ₅ OCH; H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 ch ₃ cf ₃ H H -och ₂ ch ₂ o- ch ₃ H 2 ch ₃ CF; H H -och ₂ ch ₂ o- H H 2 ch ₃ H H -och ₂ ch ₂ o- Cl Cl 2 ch ₃ cf ₃ H H -och ₂ ch ₂ o- Cl H 2 ch ₃ CF; H H -och ₂ ch ₂ o- Cl ch ₃ 2 ch ₃ CF; ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ ch ₃ 2 ch ₃ CF; ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ H 2 ch ₃ CF; ch ₃ ch ₃ -och ₂ ch ₂ o- H H 2 ch ₃ CF; ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl 2 ch ₃ CF; ch ₃ CH 3 -och ₂ ch ₂ o- Cl H 2 ch ₃ CF; ch ₃ ch ₃ -och ₂ ch ₂ o- Cl ch ₃ 2 CH 3 CF; ch ₃ H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 ch ₃ CF; ch ₃ H -och ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ CF; ch ₃ H -och ₂ ch ₂ o- H H ₂ 1 ch ₃ CF; ch ₃ H -och ₂ ch ₂ o- Cl Cl 2 1 ch ₃ CF; ch ₃ H -och ₂ ch ₂ o- Cl H 2 i ch ₃ CF; ch ₃ H -och ₂ ch ₂ o- Cl ch ₃ 2 i ch ₃ CF; H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 c ₂ h ₅ CF; H H -och ₂ ch ₂ o- ch ₃ H 2 1 c ₂ h ₅ CF;

Η H -och ₂ ch ₂ o- H H 2 ^c 2H ₅ CF; Η H -och ₂ ch ₂ o- Cl Cl 2 c ₂ h ₅ cf ₃ Η H -OCHoCHoO- A * * " Cl H 2 C ₂ H ₅ C F; Η H -OCH ₂ CH ₂ O- Cl 2 c ₂ h ₅ CF ₃ ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ ^CH 3 2 ^c 2H ₅ CF; ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₅ H 2 ^C 2H ₅ CF; ch ₃ ch ₃ -och ₂ ch ₂ o- H H 2 c ₂ h ₅ CF _? ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl 2 c ₂ h ₅ cf ₃ ch ₃ ch ₃ -och ₂ ch ₂ o- Cl H 2 c ₂ h ₅ CF ₃ ch ₃ ch ₃ -och ₂ ch ₂ o- Cl ch ₃ 2 ch ₂ ch ₂ ch ₃ ch ₃ ch ₃ H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 ch ₂ ch ₂ ch ₃ ch ₃ ch ₃ H -och ₂ ch ₂ o- ch ₃ H 2 ch ₂ ch ₂ ch ₃ ch ₃ ch ₃ H -och ₂ ch ₂ o- H H 2 ch ₂ ch ₂ ch ₃ ch ₃ ch ₃ H -och ₂ ch ₂ o- Cl Cl 2 ch ₂ ch ₂ ch ₃ ch ₃ ch ₃ H -OCH ₂ CH ₂ 0- Cl H 2 ch ₂ ch ₂ ch ₃ ch ₃ ch ₃ H -och ₂ ch ₂ o · Cl ch ₃ 2 ch ₂ ch ₂ ch ₃ ch ₃ H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 ch ₂ ch ₂ ch ₃ ch ₃ H H -och ₂ ch ₂ o- ch ₅ H 2 ch ₂ ch ₂ ch ₃ ch ₃ H H -OCH ₂ CH ₂ O- Cl Cl 2 ch ₂ ch ₂ ch ₃ ch ₃ H H -och ₂ ch ₂ o- Cl H 2 ch ₂ ch ₂ ch ₃ CH ₃ H H -och ₂ ch ₂ o- Cl ch ₃ 2 ch ₂ ch ₂ ch ₃ CH 3 ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ ch ₃ 2 ch ₂ ch ₂ ch ₃ ch ₃ ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ H ₂ ch ₂ ch ₂ ch ₃ ch ₃ ch ₃ ch ₃ -och ₂ ch ₂ o- H H 2 ch ₂ ch ₂ ch ₃ ch ₃ ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl 2 ch ₂ ch ₂ ch ₃ ch ₃ ch ₃ ch ₃ -och ₂ ch ₂ o- Cl H 2 ch ₂ ch ₂ ch ₃ ch ₃ ch ₃ ch ₃ -och ₂ ch ₂ o- Cl ch ₃ 2 ch ₂ ch ₂ ch ₃ ch ₃ ch ₃ H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 ch ₂ ch ₂ ch ₃ ch ₃ ch ₃ H -och ₂ ch ₂ o- ch ₃ H 2 ch ₂ ch ₂ ch ₃ ch ₃ ch ₃ H -och ₂ ch ₂ o- H H 2 ch ₂ ch ₂ ch ₃ CH ch ₃ H -och ₂ ch ₂ o- Cl Cl 2 ch ₂ ch ₂ ch ₃ CH; ch ₃ H -och ₂ ch ₂ o- Cl H 2 ch ₂ ch ₂ ch ₃ CH - ch ₃ H -och ₂ ch ₂ o- Cl ch ₃ 2 ch ₂ ch ₂ ch ₃ CH; H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 CH _{(CH3) 2} The H H -och ₂ ch ₂ o- ch ₃ H 2 CH _{(CH3) 2} H H H -och ₂ ch ₂ o- H H 2 CH _{(CH3) 2} H H H -och ₂ ch ₂ o- Cl Cl 2 CH _{(CH3) 2} H H H -och ₂ ch ₂ o- Cl H 2 L CH _{(CH3) 2} H

H H -och ₂ ch ₂ o- Cl ch ₃ 2 1 CH _{(CH3) 2} H ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 CH _{(CH3) 2} H ch ₃ CH; -och ₂ ch ₂ o- ch ₃ H 2 1 CH _{(CH3) 2} H ch ₃ ch ₃ -och ₂ ch ₂ o- H H 2 1 CH _{(CH3) 2} H ch ₃ CH; -och ₂ ch ₂ o- Cl Cl ₂ 1 CH _{(CH3) 2} H ch ₃ ch ₃ -och ₂ ch ₂ o- Cl H 2 I CH _{(CH3) 2} H ch ₃ ch ₃ -och ₂ ch ₂ o- Cl ch ₃ 2 1 CH _{(CH3) 2} H ch ₃ H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 CH _{(CH3) 2} H ch ₃ H -och ₂ ch ₂ o- ch ₃ H 2 1 chcch ₃ ) ₂ H ch ₃ H -och ₂ ch ₂ o- h H 2 1 CH _{(CH3) 2} H ch ₃ H -och ₂ ch ₂ o- Cl Cl 2 1 CH _{(CH3) 2} H ch ₃ H -och ₂ ch ₂ o- Cl H 2 1 CH _{(CH3) 2} H ch ₃ H -och ₂ ch ₂ o- Cl ch ₃ 2 1 CH _{(CH3) 2} H H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 c ₆ h ₅ H H H -och ₂ ch ₂ o- ch ₃ H 2 1 c ₆ h ₅ H H H -och ₂ ch ₂ o- H H 2 1 c ₆ h ₅ H H H -och ₂ ch ₂ o- Cl Cl 2 1 c ₆ h ₅ H H H -och ₂ ch ₂ o- Cl H 2 1 c ₆ h ₅ H H H -och ₂ ch ₂ o- Cl ch ₃ 2 1 H ch ₃ CH ₃ -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 C ₆ H ₅ H ch ₃ CH; -och ₂ ch ₂ o- ch ₃ H 2 1 ^c 6H ₅ H ch ₃ ch ₃ -och ₂ ch ₂ o- H H 2 1 H ch ₃ CH; -och ₂ ch ₂ o- Cl Cl 2 1 c ₆ h ₅ H ch ₃ ch ₃ -och ₂ ch ₂ o- Cl H 2 1 c ₆ h ₅ H ch ₃ ch ₃ -och ₂ ch ₂ o- Cl ch ₃ 2 ) H ch ₃ H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ^c 6H ₅ H ch ₃ H -och ₂ ch ₂ o- ch ₃ H 2 and c ₆ h ₅ H ch ₃ H -och ₂ ch ₂ o- H H 2 1 H ch ₃ H -och ₂ ch ₂ o- Cl Cl 2 1 c ₆ h ₅ H ch ₃ H -och ₂ ch ₂ o- Cl H 2 1 c ₆ h ₅ H ch ₃ H -och ₂ ch ₂ o- Cl ch ₃ 2 1 c ₆ h ₅ H H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 c ₆ h ₅ CH ₃ H H -och ₂ ch ₂ o- ch ₃ H 2 and ch ₅ H H -och ₂ ch ₂ o- H H 2 I ch ₃ H H -och ₂ ch ₂ o- Cl Cl 2 1 c ₆ h ₅ ch ₃ H H -och ₂ ch ₂ o- Cl H 2 1 c ₆ h ₅ ch ₃ H H -och ₂ ch ₂ o- Cl ch ₃ 2 1 ch ₃ ch ₃ ch ₃ -och ₂ ch ₂ o- CH ₃ ch ₃ 2 1 c ₆ h ₅ ch ₃

m

ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ H 2 c ₆ h ₅ CH ch ₃ ch ₃ -och ₂ ch ₂ o- H H 2 c ₆ h ₅ CH ch ₃ ch ₃ -och ₂ ch ₂ o · Cl Cl 2 c ₆ h ₅ ch ch ₃ ch ₃ -och ₂ ch ₂ o- Cl H 2 c ₆ h ₅ ch ch ₃ ch ₃ -och ₂ ch ₂ o- Cl CH ₃ 2 c ₆ h ₅ ch ch ₃ H -och ₂ ch ₂ o- CH ₃ ch ₃ 2 ch: ch ₃ H -och ₂ ch ₂ o- ch ₃ H 2 c ₆ h ₅ ch ch ₃ H -och ₂ ch ₂ o- H H 2 c ₆ h ₅ ch ch ₃ H -och ₂ ch ₂ o- Cl Cl 2 c ₆ h ₅ CH ch ₃ H -och ₂ ch ₂ o- Cl H 2 c ₆ h ₅ CH ch ₃ H -och ₂ ch ₂ o- Cl CH ₃ 2 c ₆ h ₅ CH H H -ch ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ 2 ch ₃ H H H -ch ₂ ch ₂ ch ₂ o- ch ₃ H 2 ch ₃ H H H -ch ₂ ch ₂ ch ₂ o- H H 2 ch ₃ H H H -ch ₂ ch ₂ ch ₂ o- Cl Cl 2 ch ₃ The H H -ch ₂ ch ₂ ch ₂ o- Cl H 2 ch ₃ H H H -ch ₂ ch ₂ ch ₂ o- Cl CH ₃ 2 ch ₃ H ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- CH ₃ ch ₃ 2 ch ₃ H ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- ch ₃ H 2 ch ₃ H ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- H H 2 ch ₃ H ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- Cl Cl 2 ch ₃ H ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- Cl H 2 ch ₃ H ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- Cl ch ₃ 2 ch ₃ H ch ₃ H -ch ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ 2 ch ₃ H ch ₃ H -ch ₂ ch ₂ ch ₂ o- ch ₃ H 2 ch ₃ H ch ₃ H -ch ₂ ch ₂ ch ₂ o- H H 2 ch ₃ H ch ₃ H -ch ₂ ch ₂ ch ₂ o- Cl Cl 2 ch ₃ H ch ₃ H -ch ₂ ch ₂ ch ₂ o- Cl H 2 ch ₃ H ch ₃ H -ch ₂ ch ₂ ch ₂ o- Cl ch ₃ 2 ch ₃ H H H -och ₂ ch ₂ ch ₂ o- CH ₃ ch ₃ 2 ch ₃ Cl H H -och ₂ ch ₂ ch ₂ o- ch ₃ H 2 ch ₃ Cl H H -och ₂ ch ₂ ch ₂ o- H H 2 ch ₃ C! H H -och ₂ ch ₂ ch ₂ o · Cl Cl 2 ch ₃ Cl H H -och ₂ ch ₂ ch ₂ o- Cl H 2 ch ₃ Cl H H -och ₂ ch ₂ ch ₂ o · Cl ch ₃ 2 ch ₃ Cl ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ 2 ch ₃ Cl ch ₃ CH ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ H 2 1 CH ₃ Cl ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- H H 2 1 ch ₃ Cl

ch ₃ ch ₃ ch ₃ ch ₃ ch ₃ ch ₃ ch ₃ ch ₃ CH ₃ CH ₃ CH ₃ H H H H H -OCH ₂ CH ₂ CH ₂ O- -OCH ₂ CH ₂ CH ₂ O- -OCH ₂ CH ₂ CH ₂ O- -OCH ₂ CH ₂ CH ₂ O- -OCH ₂ CH ₂ CH ₂ O- -OCH ₂ CH ₂ CH ₂ O- -OCH ₂ CH ₂ CH ₂ O- -OCH ₂ CH ₂ CH ₂ O- Cl Cl Cl ch ₃ ch ₃ H Cl Cl Cl H ch ₃ ch ₃ H H Cl H 2 2 2 2 2 2 2 2 1 1 1 1 1 1 1 1 CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ Cl Cl Cl Cl Cl Cl Cl Cl ch ₃ H -och ₂ ch ₂ ch ₂ o- Cl CH ' 2 1 ch ₃ Cl H H -och ₂ ch ₂ o- CH ₃ ch ₃ 2 1 c ₂ h ₅ Cl H H -och ₂ ch ₂ o- ch ₃ H 2 1 c ₂ h ₅ Cl H H -och ₂ ch ₂ o- H H 2 1 c ₂ h ₅ Cl H H -och ₂ ch ₂ o- Cl Cl 2 1 c ₂ h ₅ Cl H H -och ₂ ch ₂ o- Cl H 2 1 c ₂ h ₅ Cl H H -och ₂ ch ₂ o- Cl ch ₃ 2 1 c ₂ h ₅ Cl ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 c ₂ h ₅ Cl ch ₃ ch ₃ -OCH ₂ CH ₂ O- ch ₃ H 2 1 c ₂ h ₅ Cl ch ₃ ch ₃ -och ₂ ch ₂ o- H H 2 1 c ₂ h ₅ Cl ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl 2 1 c ₂ h ₅ Cl ch ₃ CH; -och ₂ ch ₂ o- Cl H, 2 1 c ₂ h ₅ Cl čh ₃ CH ₃ -och ₂ ch ₂ o- Cl ch ₃ 2 1 ^c 2 ^H 5 Cl ch ₃ H -OCH ₂ CH ₂ O- ch ₃ ch ₃ 2 1 c ₂ h ₅ Cl ch ₃ H -och ₂ ch ₂ o- ch ₃ H 2 1 c ₂ h ₅ Cl ch ₃ H -och ₂ ch ₂ o- H H 2 1 c ₂ h ₅ Cl ch ₃ H -och ₂ ch ₂ o- Cl Cl 2 1 c ₂ h ₅ Cl ch ₃ H -och ₂ ch ₂ ch ₂ o- Cl H 2 1 c ₂ h ₅ Cl ch ₃ H -och ₂ ch ₂ o- Cl ch ₃ 2 1 c ₂ h ₅ Cl H H -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ H H H och ₂ ch ₂ ch ₂ o ch ₃ H 2 I ch ₃ H H H och ₂ ch ₂ ch ₂ o H H 2 1 ch ₃ H H H och ₂ ch ₂ ch ₂ o Cl Cl 2 1 ch ₃ H H H och ₂ ch ₂ ch ₂ o Cl H 2 1 ch ₃ H H H och ₂ ch ₂ ch ₂ o Cl ch ₃ 2 1 ch ₃ H ch ₃ CH ₃ och ₂ ch ₂ ch ₂ o ch ₃ ch ₃ 2 1 ch ₃ H ch ₃ ch ₃ och ₂ ch ₂ ch ₂ o ch ₃ H 2 1 ch ₃ H ch ₃ ch ₃ och ₂ ch ₂ ch ₂ o H H 2 1 ch ₃ H ch ₃ ch ₃ och ₂ ch ₂ ch ₂ o Cl Cl 2 1 ch ₃ H ch ₃ ch ₃ och ₂ ch ₂ ch ₂ o Cl H 2 1 ch ₃ H

ch ₃ ch ₃ ch ₃ ch ₃ ch ₃ H H H OCH ₂ CH ₂ CH ₂ O ₂ ch ₂ ch ₂ o ₂ ch ₂ ch ₂ o ₂ ch ₂ ch ₂ o Cl ch ₃ ch ₃ H ^C H ₃ CH ₃ H H 2 2 2 2 1 1 1 1 ch ₃ ch ₃ ch ₃ ch ₃ H h ' H H ch ₃ H och ₂ ch ₂ ch ₂ o Cl Cl 2 1 ch ₃ H ch ₃ H och ₂ ch ₂ ch ₂ o Cl H 2 l ch ₃ H ch ₃ H och ₂ ch ₂ ch ₂ o Cl ch ₃ 2 1 ch ₃ H H H -sch ₂ ch ₂ s- ch ₃ ch ₃ 2 1 ch ₃ H H H -sch ₂ ch ₂ s- ch ₃ ch ₃ 0 1 ch ₃ H H H -sch ₂ ch ₂ s- ch ₃ H 2 1 ch ₃ H H H -sch ₂ ch ₂ s- H H 2 1 ch ₃ H H H -sch ₂ ch ₂ s- Cl Cl 2 1 ch ₃ H H H -sch ₂ ch ₂ s- Cl H 2 1 ch ₃ H H H -sch ₂ ch ₂ s- Cl ch ₃ 2 1 ch ₃ H ch ₃ ch ₃ -sch ₂ ch ₂ s- CK ₃ ch ₃ 2 1 ch ₃ H ch ₃ ch ₃ -sch ₂ ch ₂ s- ch ₃ H 2 1 ch ₃ H ch ₃ ch ₃ -sch ₂ ch ₂ s- H H 2 1 ch ₃ H ch ₃ CHS -sch ₂ ch ₂ s- Cl Cl 2 1 ch ₃ H ch ₃ ch ₃ -sch ₂ ch ₂ s- Cl H 2 1 ch ₃ H ch ₃ ch ₃ -sch ₂ ch ₂ s- Cl ch ₃ 2 1 ch ₃ H ch ₃ H -sch ₂ ch ₂ s- ch ₃ ch ₃ 2 1 ch ₃ H ch ₃ H -sch ₂ ch ₂ s- ch ₃ H 2 1 ch ₃ H ch ₃ H -sch ₂ ch ₂ s- H H 2 1 ch ₃ H ch ₃ H -sch ₂ ch ₂ s- Cl Cl 2 1 ch ₃ H ch ₃ H -sch ₂ ch ₂ s- Cl H 2 1 ch ₃ H ch ₃ H -sch ₂ ch ₂ s- Cl ch ₃ 2 1 ch ₃ H H H -sch ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ H H H -sch ₂ ch ₂ o- ch ₃ ch ₃ 0 1 ch ₃ H H H -sch ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ H H H -sch ₂ ch ₂ o- H H 2 1 ch ₃ H H H -sch ₂ ch ₂ o- Cl Cl 2 1 ch ₃ H H H -sch ₂ ch ₂ o- Cl H 2 1 ch ₃ .:} H H -sch ₂ ch ₂ o- Cl ch _{3 2} 1 ch ₃ H ch ₃ ch ₃ -sch ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ H ch ₃ ch ₃ -sch ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ H ch ₃ ch ₃ -sch ₂ ch ₂ o- H H 2 1 ch ₃ H ch ₃ ch ₃ -sch ₂ ch ₂ o- Cl Cl 2 1 ch ₃ H ch ₃ ch ₃ -sch ₂ ch ₂ o- Cl H 2 1 CH · ·} H

CH ₃ ch ₃ -sch ₂ ch ₂ o- Cl ch _{3 2} 1 ch ₃ H ch ₃ h -sch ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ H CH 3 h -sch ₂ ch ₂ o · ch ₃ h ₂ 1 CH 3 H CH ₃ H -sch ₂ ch ₂ o- H H 2 1 ch ₃ H ch ₃ H -sch ₂ ch ₂ o- Cl Cl ₂ 1 ch ₃ H ch ₃ H -sch ₂ ch ₂ o- Cl H 2 1 ch ₃ H ch ₃ H -sch ₂ ch ₂ o- Cl ch ₃ 2 1 ch ₃ H H H -sch ₂ ch ₂ ch ₂ s- ch ₃ ch ₃ 2 1 ch ₃ H H H -sch ₂ ch ₂ ch ₂ s- ch ₃ H 2 1 ch ₃ H H H -sch ₂ ch ₂ ch ₂ s- H H 2 l ch ₃ H H H -sch ₂ ch ₂ ch ₂ s- Cl Cl 2 1 ch ₃ H H H -sch ₂ ch ₂ ch ₂ s- Cl H 2 1 ch ₃ H H H -sch ₂ ch ₂ ch ₂ s- Cl ch ₃ 2 1 ch ₃ H CH j ch ₃ -sch ₂ ch ₂ ch ₂ s- ch ₃ ch ₃ 2 1 ch ₃ H CH ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- ch ₃ H 2 1 ch ₃ H CH ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- H H ₂ and ch ₃ H CH ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- Cl Cl 2 1 ch ₃ H ch ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- Cl H 2 1 ch ₃ H ch ₃ ch ₃ -sch ₂ ch ₂ ch ₂ s- Cl CH ₃ 2 1 ch ₃ H ch ₃ H -sch ₂ ch ₂ ch ₂ s- CH ₃ ch ₃ 2 1 ch ₃ H ch ₃ H -sch ₂ ch ₂ ch ₂ s- ch ₃ H 2 1 ch ₃ H ch ₃ H -sch ₂ ch ₂ ch ₂ s- H H 2 1 ch ₃ H CH ₃ H -sch ₂ ch ₂ ch ₂ s- Cl Cl 0 4th 1 ch ₃ H ch ₃ H -sch ₂ ch ₂ ch ₂ s- Cl H 2 1 ch ₃ H ch ₃ H -sch ₂ ch ₂ ch ₂ s- Cl ch ₃ 2 1 ch ₃ H H H 0X0 ch ₃ ch ₃ 2 1 ch ₃ H H H 0X0 ch ₃ H 2 1 ch ₃ H H H 0X0 Cl Cl 2 1 ch ₃ The H H 0X0 Cl H 2 1 ch ₃ H H H 0X0 Cl ch ₃ Second 1 ch ₃ H ch ₃ CH ₃ 0X0 ch ₃ ch ₃ 2 1 ch ₃ H ch ₃ ch ₃ 0X0 ch ₃ H 2 1 ch ₃ H ch ₃ ch ₃ 0X0 H H 2 1 ch ₃ H ch ₃ ch ₃ 0X0 Cl Cl 2 1 ch ₃ The ch ₃ ch ₃ 0X0 Cl H 2 1 ch ₃ H ch ₃ ch ₃ 0X0 Cl ch ₃ 2 1 ch ₃ H ch ₃ H 0X0 ch ₃ ch ₃ 2 1 ch ₃ H ch ₃ H 0X0 ch ₃ H 2 1 ch ₃ H

CH ₃ h 0X0 H H *> ch ₃ CH ₃ h 0X0 Cl Cl 2 ch ₃ CH ₃ h 0X0 Cl H 2 ch ₃ CH ₃ H 0X0 Cl ch ₃ 2 ch ₃ H H 0X0 CH ₃ ch ₃ 1 ch ₃ H H 0X0 ch ₃ H ] ch ₃ H H 0X0 H H ] ch ₃ H H 0X0 Cl Cl 1 ch ₃ H H 0X0 Cl H 1 ch ₃ H H 0X0 Cl ch ₃ ] ch ₃ CH ₃ ch ₃ 0X0 CH ₃ ch ₃ 1 ch ₃ ch ₃ ch ₃ 0X0 ch ₃ H 1 ch ₃ ch ₃ ch ₃ 0X0 h H 1 ch ₃ ch ₃ ch ₃ 0X0 Cl Cl 1 ch ₃ ch ₃ ch ₅ 0X0 Cl H 1 ch ₃ ch ₃ ch ₃ 0X0 Cl ch ₃ 1 ch ₃ ch ₃ H 0X0 CH ₃ ch ₃ 1 ch ₃ ch ₃ H 0X0 ch ₃ H ] ch ₃ ch ₃ H 0X0 H H ] ch ₃ ch ₃ H 0X0 Cl Cl 1 ch ₃ CH 3 H 0X0 Cl H ] 1 ch ₃ ch ₃ H 0X0 Cl ch ₃ ] 1 CH ₃ table 5

Η

Η

Η

H

Η

H

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Η

Κ

Η

Η

Η

_R 3a _R 3b R ¹ R ² R ⁴ R ⁵ R ⁶ n m H H -och ₂ ch ₂ o- ch ₃ CH ;, OH 2 1 H H -och ₂ ch ₂ o- ch ₃ H OH 2 1 H H -och ₂ ch ₂ o- H H OH 2 1 H H -och ₂ ch ₂ o- Cl Cl OH 2 . b H H -och ₂ ch ₂ o- Cl H OH 2 1 H H -OCH ₂ CH ₂ O- Cl ch ₃ OH .2 1 H H -OCH ₂ CH ₂ O- · no ₂ H OH 2 1

ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ ch ₃ OH 2 1 ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ H OH ₂ 1 CH ₃ ch ₃ -och ₂ ch ₂ o- H H OH about 1 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl OH ₂ 1 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl H OH ₂ 1 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl ch ₃ OH ₂ 1 ch ₃ H -och ₂ ch ₂ o- ch ₃ ch ₃ OH ₂ 1 ch ₃ H -och ₂ ch ₂ o- ch ₃ H OH ₂ 1 CH ₃ H -och ₂ ch ₂ o- H H OH ₂ 1 ch ₃ H -och ₂ ch ₂ o- Cl Cl OH 2 1 ch ₃ H -och ₂ ch ₂ o- Cl H OH 2 1 ch ₃ H -och ₂ ch ₂ o- Cl ch ₃ OH 2 1 h H -OCH ₂ CH (CH ₃ ) 0 - ch ₃ ch ₃ OH ₂ 1 h H -OCH ₂ CH (CH ₃ ) O - ch ₃ H OH ₂ 1 H H -OCH ₂ CH (CH ₃ ) 0 - h H OH ₂ 1 H H -OCH ₂ CH (CH ₃ ) 0 - Cl Cl OH ₂ 1 H H -OCH ₂ CH (CH ₃ ) O - Cl H OH 2 1 H H -OCH ₂ CH (CH ₃ ) 0 - Cl CH ₃ OH 2 ] ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) 0 - ch ₃ ch ₃ OH 2 1 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - ch ₃ H OH 2 1 ch ₃ CH ₃ -OCH ₂ CH (CH ₃ ) 0 - h H OH 2 1 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - Cl Cl OH 2 1 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - Cl H OH 2 ] ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) 0 - Cl ch ₃ OH 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) 0 - ch ₃ ch ₃ OH 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) O - ch ₃ H OH 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) 0 - H H OH 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) O - Cl Cl OH 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) 0 - Cl H OH 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) 0 - Cl CH ₃ OH 2 1 H H -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ OH '2 1 H H -och ₂ ch ₂ ch ₂ o- ch ₃ H OH 2 1 H H -och ₂ ch ₂ ch ₂ o- H H OH 2 1 H H -och ₂ ch ₂ ch ₂ o- Cl Cl OH 2 1 H H -och ₂ ch ₂ ch ₂ o- Cl H OH 2 1 H H -och ₂ ch ₂ ch ₂ o- Cl ch ₃ OH 2 1 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ OH 2 1 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ H OH 2 1

CH ;, ch ₃ -OCH ₂ CH ₂ CH ₂ O- H H OH 2 1 CH ch ₃ -OCHoCHqCHoO- Cl Cl OH 2 1 CH ₅ ch ₃ -och ₂ ch ₂ ch ₂ o- Cl H OH ₂ 1 CH; ch ₃ -och ₂ ch ₂ ch ₂ o- Cl ch ₃ OH ₂ 1 ch ₃ H -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ OH 2 1 ch ₃ H -OCH ₂ CH ₂ CH ₂ O- CH3 H OH 2 1 ch ₃ H -och ₂ ch ₂ ch ₂ o- H H OH 2 1 ch ₃ H -och ₂ ch ₂ ch ₂ o- Cl Cl OH 2 1 ^C «3 H -och ₂ ch ₂ ch ₂ o- Cl H OH 2 1 ch ₃ H -och ₂ ch ₂ ch ₂ o- Cl ch ₃ OH 2 1 H H -ch ₂ ch ₂ ch ₂ o- ch ₃ <= 3 * OH 2 1 H H -ch ₂ ch ₂ ch ₂ o- ch ₃ H OH 2 1 H H -ch ₂ ch ₂ ch ₂ o- H H OH 2 1 H H -ch ₂ ch ₂ ch ₂ o- Cl Cl OH 2 1 H H -ch ₂ ch ₂ ch ₂ o- Cl H OH 2 1 H H -ch ₂ ch ₂ ch ₂ o- Cl CH ₃ OH 2 1 ^CH 5 ch ₃ -ch ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ OH 2 1 CH3 ch ₃ -ch ₂ ch ₂ ch ₂ o- ch ₃ H OH 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- H H OH 2 1 CH ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- Cl Cl OH 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- Cl H OH 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- Cl CH ₃ OH 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ o- CH ₃ ch ₃ OH 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ o- ch ₃ H OH 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ o- H H OH 2 ] ch ₃ H -ch ₂ ch ₂ ch ₂ o- Cl Cl OH 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ o- Cl H OH 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ o- Cl ch ₃ OH 2 1 H H -och ₂ ch ₂ o- ch ₃ ch ₃ OH 2 0 H H -och ₂ ch ₂ o- ch ₃ H OH 2 0 H H -och ₂ ch ₂ o- H H OH 2 0 H H -och ₂ ch ₂ o- C Cl OH 2 0 H H -och ₂ ch ₂ o- Cl H OH 2 0 H H -och ₂ ch ₂ o- Cl ck ₃ OH 2 0 ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ ch ₃ OH 2 0 ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ H OH 2 0 ch ₃ ch ₃ -och ₂ ch ₂ o- H H OH 2 0 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl OH 2 0

ch ₃ ch ₃ -och ₂ ch ₂ o- Cl H OH ₂ 0 ch ₃ ch ₃ -OCH ₂ CH ₂ O · Cl ch ₃ OH 2 0 ch ₃ H -och ₂ ch ₂ o- ch ₃ ch ₃ OH 2 0 ch ₃ H -och ₂ ch ₂ o- ch ₃ H OH 2 0 ch ₃ H -och ₂ ch ₂ o- H H OH 2 0 ch ₃ H -och ₂ ch ₂ o- Cl Cl OH 2 0 CH ₃ H -och ₂ ch ₂ o- Cl H OH 2 0 ch ₃ H -och ₂ ch ₂ o- Cl ch ₃ OH 2 0 H H -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ OH 2 0 H H -OCH ₂ CH (CH ₃ ) O - ch ₃ H OH 2 0 H H -OCH ₂ CH (CH ₃ ) O - H H OH 2 0 H H -OCH ₂ CH (CH ₃ ) 0 - Cl Cl OH 2 0 H H -OCH ₂ CH (CH ₃ ) 0 - Cl H OH 2 0 H H -OCH ₂ CH (CH ₃ ) O - Cl ch ₃ OH 2 0 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ OH 2 0 ch ₃ -OCH ₂ CH (CH ₃ ) 0 - ch ₃ H OH 2 0 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) 0 - H H OH 2 0 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - Cl Cl OH 2 0 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - Cl H OH 2 0 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) 0 - Cl ch ₃ OH 2 0 ch ₃ H -OCH ₂ CH (CH ₃ ) O - ch ₃ . ch ₃ OH 2 0 ch ₃ H -OCH ₂ CH (CH ₃ ) 0 - ch ₃ H OH 2 0 ch ₃ H -OCH ₂ CH (CH ₃ ) 0 - H H OH 2 0 ch ₃ H -OCH ₂ CH (CH ₃ ) O - Cl Cl OH 2 0 ch ₃ H -OCH ₂ CH (CH ₃ ) O - Cl H OH 2 0 ch ₃ H -OCH ₂ CH (CH ₃ ) O - Cl CH ₃ OH 2 0 h H -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ OH 2 0 H H -och ₂ ch ₂ ch ₂ o- ch ₃ H OH 2 0 H H -och ₂ ch ₂ ch ₂ o- H H OH 2 0 H H -och ₂ ch ₂ ch ₂ o- Cl Cl OH 2 0 H H -och ₂ ch ₂ ch ₂ o- Cl H OH 2 0 H H -OCH ₂ CH ₂ CH ₂ - Cl ch ₃ OH 2 0 ch ₃ ch ₃ -OCH ₂ CH ₂ CH ₂ O- ch ₃ ch ₃ OH 2 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ H OH 2 . 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- H H OH 2 0 ch ₃ ch ₃ -OCH ₂ CH ₂ CH ₂ O- Cl Cl OH 2 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- Cl H OH 2 0 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- Cl ch ₃ OH 2 0

ch ₃ H -OCH ₂ CH ₂ CH ₂ O- ch ₃ ch ₃ OH 2 0 ch ₃ H -och ₂ ch ₂ ch ₂ o- ch ₃ The OH 2 0 ch ₃ H -och ₂ ch ₂ ch ₂ o- H H OH 2 0 ch ₃ H -OCH ₂ CH ₂ CH ₂ · Cl Cl OH ₂ 0 ch ₃ H -och ₂ ch ₂ ch ₂ o- Cl H OH 2 0 ch ₃ H -och ₂ ch ₂ ch ₂ o- Cl ch ₃ OH 2 0 H H -sch ₂ ch ₂ s- ch ₃ ch ₃ OH 2 0 H H -sch ₂ ch ₂ s- ch ₃ ch ₃ OH 0 0 H H -sch ₂ ch ₂ s- ch ₃ H OH 2 0 H H -sch ₂ ch ₂ s- H H OH 2 0 H H -sch ₂ ch ₂ s- Cl Cl OH 2 0 H H -sch ₂ ch ₂ s- Cl H OH 2 0 H H -sch ₂ ch ₂ s- Cl ch ₃ OH 2 0 H H -sch ₂ ch ₂ s- no ₂ H OH 2 0 ch ₃ ch ₃ -sch ₂ ch ₂ s- ch ₃ «3 OH 2 0 ch ₃ ch ₃ -sch ₂ ch ₂ s- ch ₃ H OH 2 0 ch ₃ ch ₃ -sch ₂ ch ₂ s- H H OH 2 0 ^ 3 ch ₃ -sch ₂ ch ₂ s- Cl Cl OH 2 0 ^CH 5 ch ₃ -sch ₂ ch ₂ s- Cl H OH 2 0 ch ₃ ch ₃ -sch ₂ ch ₂ s- Cl ch ₃ OH 2 0 ch ₃ H -sch ₂ ch ₂ s- ch ₃ Cri ₃ OH 2 0 ch ₃ H -sch ₂ ch ₂ s- ch ₃ H OH 2 0 ch ₃ H -sch ₂ ch ₂ s- H H OH 2 0 ch ₃ H -sch ₂ ch ₂ s- Cl Cl OH 2 0 ch ₃ H -sch ₂ ch ₂ s- Cl H OH 2 0 ch ₃ H -sch ₂ ch ₂ s- Cl ch ₃ OH 2 0 H H -sch ₂ ch ₂ o- ch ₃ ch ₃ OH 2 0 H H -sch ₂ ch ₂ o- ch ₃ ch ₃ OH 0 0 H H 0X0 ch ₃ ch ₃ OH 2 1 H H 0X0 ch ₃ H OH 2 1 H H 0X0 H H OH 2 H H 0X0 Cl Cl OH 2 H H 0X0 Cl H OH 2 H H 0X0 Cl CK ₃ OH • 2 H H 0X0 no ₂ H OH 2 ch ₃ ch ₃ 0X0 ch ₃ ch ₃ OH 2 ch ₃ ch ₃ 0X0 ch ₃ H OH 2 ch ₃ ch ₃ 0X0 H H OH 2

ch ₃ ch ₃ 0X0 Cl Cl OH 2 I ch ₃ ch ₃ 0X0 Cl H OH 2 1 ch ₃ ch ₃ 0X0 Cl ch ₃ OH n 1 ch ₃ H 0X0 ch ₃ ch ₃ OH n 1 ch ₃ H 0X0 ch ₃ H OH 2 1 ch ₃ H 0X0 H H OH 2 ] ch ₃ H 0X0 Cl Cl OH *> 1 ch ₃ H 0X0 Cl H OH 2 ch ₃ H 0X0 Cl ch ₃ OH 2 1 H H 0X0 ch ₃ ch ₃ OH 1 1 H H 0X0 ch ₃ H OH 1 1 H H 0X0 H H OH ] ] H H 0X0 Cl Cl OH 1 1 H H 0X0 Cl H OH 1 1 H H 0X0 Cl ch ₃ OH 1 1 ch ₃ CH 0X0 ^C H ₃ ch ₃ OH 1 ] ch ₃ ch ₃ 0X0 ch ₃ H OH 1 1 ck ₃ ch ₃ 0X0 H H OH 1 1 ch ₃ ch ₅ 0X0 Cl Cl OH 1 1 ch ₃ ch ₃ 0X0 Cl H OH ] 1 ch ₃ ch ₃ 0X0 Cl ch ₃ OH 1 ] ch ₃ H 0X0 ch ₃ ch ₃ OH 1 1 ch ₃ H 0X0 ch ₃ H OH 1 1 ch ₃ H 0X0 H H OH 1 ] ch ₃ H 0X0 Cl Cl OH 1 1 ch ₃ H 0X0 Cl H OH 1 1 ch ₃ H 0X0 Cl ch ₃ OH 1 1 Table 6 1 f R ’χϊ R ⁴ 0 OH (ym ABOUT N- ch ₂ ch ₃ R ^3a - _R 3b R ⁵ r33 R ^3b rl R ² R ⁴ R ³ n m H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 H H -och ₂ ch ₂ o- ch ₃ H ₂ 1

Η H -OCH ₂ CH ₂ O- H H ₂ 1 Η H -och ₂ ch ₂ o- Cl Cl 2 1 Η H -och ₂ ch ₂ o- Cl H ₂ and Η H -och ₂ ch ₂ o- Cl ch _{3 2} 1 Η H -och ₂ ch ₂ o- no ₂ H 2 1 ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ ch ₃ -och ₂ ch ₂ o- H H 2 1 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl 2 1 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl H 2 1 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl ch ₃ 2 1 ch ₃ H -och ₂ ch ₂ o · ch ₃ ch ₃ 2 1 ch ₃ H -och ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ H -och ₂ ch ₂ o- H H 2 ] ch ₃ H -och ₂ ch ₂ o- Cl Cl 2 1 ch ₃ H -och ₂ ch ₂ o- Cl H 2 1 CH3 H -och ₂ ch ₂ o- Cl ch ₃ 2 1 H H -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ 2 1 H H -OCH ₂ CH (CH ₃ ) O - ch ₃ H 2 1 H H -OCH ₂ CH (CH ₃ ) O - H H 2 ] H H -OCH ₂ CH (CH ₃ ) O - Cl Cl 2 1 H H -OCH ₂ CH (CH ₃ ) O - Cl H 2 1 H H -OCH ₂ CH (CH ₃ ) O - Cl ch ₃ 2 1 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ 2 ] ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - ch ₃ H 2 1 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - H H 2 1 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) O - Cl Cl 2 1 ch ₃ . ch ₃ -OCH ₂ CH (CH ₃ ) O - Cl H 2 1 ch ₃ ch ₃ -OCH ₂ CH (CH ₃ ) 0 - Cl ch ₃ 2 ] ch ₃ H -OCH ₂ CH (CH ₃ ) 0 - ch ₃ ch ₃ 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) O - ch ₃ H 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) 0 - H H 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) O - Cl Cl 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) 0 - Cl H 2 1 ch ₃ H -OCH ₂ CH (CH ₃ ) O - Cl ch ₃ 2 1 H H -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ 2 1 H H -och ₂ ch ₂ ch ₂ o- ch ₃ H 2 1 H H -och ₂ ch ₂ ch ₂ o- H H 2 1

Η H -OCH ₂ CH ₂ CH ₂ O- Cl Cl 2 1 Η H -OCH ₂ CH ₂ CH ₂ O · Cl H 2 1 Η H • ₂ ch ₂ ch ₂ o- Cl ch ₃ 2 1 CH ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ 2 1 CH ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- H H 2 1 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- Cl Cl 2 1 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- Cl H ₂ 1 ch ₃ ch ₃ -och ₂ ch ₂ ch ₂ o- Cl ch ₃ 2 1 ch ₃ H -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ H -och ₂ ch ₂ ch ₂ o- ch ₃ H 2 1 ch ₃ H -och ₂ ch ₂ ch ₂ o- H H 2 1 ch ₃ H -och ₂ ch ₂ ch ₂ o- Cl Cl ₂ 1 CH 3 H -och ₂ ch ₂ ch ₂ o- Cl H 2 1 ch ₃ H -och ₂ ch ₂ ch ₂ o- Cl ch ₃ 2 ] H H -ch ₂ ch ₂ ch ₂ o- ch ₃ ch _{3 2} 1 H H -ch ₂ ch ₂ ch ₂ o- ch ₃ H 2 1 H H -ch ₂ ch ₂ ch ₂ o- H H 2 1 H H -ch ₂ ch ₂ ch ₂ o- Cl Cl 2 1 H H -ch ₂ ch ₂ ch ₂ o- Cl H 2 1 H H -ch ₂ ch ₂ ch ₂ o- Cl ch ₃ 2 ] ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ™ 3 CH ₃ -ch ₂ ch ₂ ch ₂ o- CH 3 H 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- The H 2 1 ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- Cl Cl 2 ] ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- Cl H 2 ] ch ₃ ch ₃ -ch ₂ ch ₂ ch ₂ o- Cl ch ₃ 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ o- ch ₃ H 2 1 ^ABOUT! 3 H -ch ₂ ch ₂ ch ₂ o- H H 2 1 ch ₃ . H -ch ₂ ch ₂ ch ₂ o- Cl Cl 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ o- Cl H 2 1 ch ₃ H -ch ₂ ch ₂ ch ₂ o- Cl ch _{3 2} 1 H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 0 H H -och ₂ ch ₂ o- ch ₃ H 2 0 H H -och ₂ ch ₂ o- H H 2 0 H H -och ₂ ch ₂ o- Cl Cl ₂ 0 H H -och ₂ ch ₂ o- Cl H 2 0

Η H -och ₂ ch ₂ o- Cl ch _{3 2} 0 ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ ch _{3 2} 0 ch ₃ ch ₃ -OCH ₂ CH ₂ O- ch ₃ H 2 0 ch ₃ ch ₃ -och ₂ ch ₂ o- H H ₂ 0 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl ₂ 0 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl H 2 0 ch ₃ ch ₃ -och ₂ ch ₂ o- Cl ch ₃ 2 0 ch ₃ H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 0 ch ₃ H -och ₂ ch ₂ o- ch ₃ H ₂ 0 ch ₃ H -och ₂ ch ₂ o- H H 2 0 ch ₃ H -och ₂ ch ₂ o- Cl Cl 2 0 ch ₃ H -och ₂ ch ₂ o- Cl H 2 0 ch ₃ H -och ₂ ch ₂ o- Cl CH ₃ 2 0 H H 0X0 no ₂ H ₂ 1 ch ₃ ch ₃ 0X0 ch ₃ ch ₃ 2 1 ch ₃ ch ₃ 0X0 ch ₃ H ₂ 1 ch ₃ ch ₃ 0X0 H H 2 1 ch ₃ 0X0 Cl Cl 2 1 ch ₃ ch ₃ 0X0 Cl H 2 1 ch ₃ ch ₃ 0X0 Cl ch ₃ 2 1 ch ₃ H 0X0 ch ₃ ch ₃ 2 1 ch ₃ H 0X0 ch ₃ H 2 1 ch ₃ H 0X0 H H 2 1 ch ₃ H 0X0 Cl Cl 2 ] ch ₃ H 0X0 Cl H 2 1 ch ₃ H 0X0 Cl CH ₃ 2 1 H H 0X0 ch ₃ ch ₃ 1 1 H H 0X0 ch ₃ H 1 1 H H 0X0 H H 1 1 H H 0X0 Cl Cl 1 1 H H 0X0 Cl H 1 1 H H 0X0 Cl ch ₃ 1 1 ch ₃ 0X0 ch ₃ ch ₃ 1 1 ch ₃ ch ₃ 0X0 ch ₃ H 1 1 ch ₃ ch ₃ 0X0 H H ] 1 ch ₃ ch ₃ 0X0 Cl Cl 1 1 ch ₃ ch ₃ 0X0 Cl H 1 1 ch ₃ ch ₃ 0X0 Cl ch ₃ 1 1

ch ₃ H 0X0 ch ₃ CH ₃ 1 l ch ₃ H 0X0 ch ₃ H l 1 ch ₃ H 0X0 H H 1 1 ch ₃ H 0X0 Cl Cl 1 1 ch ₃ H 0X0 Cl H 1 1 ch ₃ H 0X0 Cl CH ₃ 1 1

_R 3a _R 3b R ³ R ² R ⁴ r5 R ⁶ n m x H H -OCH ₂ CH ₂ O- ch ₃ ch ₃ OH ₂ 1 NSO ₂ CH ₃ H H -och ₂ ch ₂ o- ch ₃ H OH 2 1 nso ₂ ch ₃ H H -och ₂ ch ₂ o- H H OH 2 1 nso ₂ ch ₃ H H -och ₂ ch ₂ o- Cl Cl OH 2 1 nso ₂ ch ₃ H H -OCH ₂ CH ₂ O- Cl H OH 2 1 nso ₂ ch ₃ H H -och ₂ ch ₂ o- Cl ch ₃ OH 2 1 nso ₂ ch ₃ H H -och ₂ ch ₂ o- no ₂ H OH 2 1 nso ₂ ch ₃ H H -OCH ₂ CH ₂ O- ch ₃ ch ₃ OH 2 1 0 H H -och ₂ ch ₂ o- ch ₃ H OH 2 I about H H -och ₂ ch ₂ o- H H OH 2 ] 0 H H OCH ₂ CH _{2 O:} Cl Cl OH 2 1 about H H -och ₂ ch ₂ o- Cl H OH 2 1 0 H H -och ₂ ch ₂ o- Cl ch ₃ OH 2 1 about H H -och ₂ ch ₂ o- CH ₃ ch ₃ OH 2 1 NH H H -och ₂ ch ₂ o- ch ₃ H OH 2 1 NH H H -och ₂ ch ₂ o- H H OH 2 1 NH H H -och ₂ ch ₂ o- Cl Cl OH 2 1 NH H H -och ₂ ch ₂ o- Cl H OH 2 1 NH H H -och ₂ ch ₂ o- Cl ch ₃ OH 2 1 NH H H -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ OH 2 1 nso ₂ ch ₃ H H -OCH ₂ CH (CH ₃ ) O - ch ₃ H OH 2 1 nso ₂ ch ₃

Η Η -OCH ₂ CH (CH ₃ ) 0 - H H OH 2 1 NSOiCK ;, Η Η -OCH ₂ CH (CH ₃ ) 0 - Cl Cl OH 2 1 NSO ₂ CH ₃ Η Η -OCH ₂ CH (CH ₃ ) O - Cl H OH Ί 1 nso ₂ ch _? Η Η -OCH ₂ CH (CH ₃ ) 0 - Cl ch ₃ OH T 1 nso ₂ ch-. Η ch ₃ -OCH ₂ CH (CH ₃ ) 0 - ch ₃ CH OH 2 I 0 Η ch ₃ -OCH ₂ CH (CH ₃ ) 0 - ch ₃ H OH 2 1 0 Η ch ₃ -OCH ₂ CH (CH ₃ ) 0 - H H OH 2 1 0 Η ch ₃ -OCH ₂ CH (CH ₃ ) 0 - Cl Cl OH 2 1 0 Η ch ₃ -OCH ₂ CH (CH ₃ ) 0 - Cl H OH 2 1 0 Η ch ₃ -OCH ₂ CH (CH ₃ ) 0 - Cl ch ₃ OH 2 1 0 Η H -OCH ₂ CH (CH ₃ ) O - ch ₃ ch ₃ OH ₂ 1 NH Η H -OCH ₂ CH (CH ₃ ) 0 - ch ₃ H OH 2 1 NH Η H -OCH ₂ CH (CH ₃ ) 0 - H H OH 2 1 NH Η H -OCH ₂ CH (CH ₃ ) O - Cl Cl OH. n 1 NH Η H -OCH ₂ CH (CH ₃ ) 0 - Cl H OH ₂ 1 NH Η H -OCH ₂ CH (CH ₃ ) O - Cl ch ₃ OH 2 1 NH Η H -och ₂ ch ₂ ch ₂ o- ch ₃ ch ₃ OH 2 ] NSO ₂ CH ₃ Η H -och ₂ ch ₂ ch ₂ o- ch ₃ H OH ₂ ] nso ₂ ch ₃ Η H -och ₂ ch ₂ ch ₂ o- H H OH 2 1 nso ₂ ch ₃ Η H -och ₂ ch ₂ ch ₂ o- Cl Cl OH ₂ 1 nso ₂ ch ₃ Η H 0X0 ch ₃ ch ₃ OH 2 1 nso ₂ ch ₃ Η H 0X0 ch ₃ H OH 2 1 nso ₂ ch ₃ Η H 0X0 H H OH 2 J nso ₂ ch ₃ Η H 0X0 Cl Cl OH 2 1 nso ₂ ch ₃ Η H 0X0 Cl H OH 2 1 nso ₂ ch ₃ Η H 0X0 Cl ch ₃ OH 2 1 nso ₂ ch ₃ Η H 0X0 no ₂ H OH 2 1 nso ₂ ch ₃ Η H 0X0 ch ₃ ch ₃ OH 2 1 about Η H 0X0 ch ₃ H OH 2 1 0 Η H 0X0 H H OH ₂ 1 0 Η H 0X0 Cl Cl OH 2 1 0 Η H 0X0 Cl H OH ₂ I 0 Η H 0X0 Cl ch ₃ OH ₂ 1 0 Η H 0X0 ch ₃ ch ₃ OH ₂ 1 NH Η H 0X0 ch ₃ H OH 2 1 NH Η H 0X0 H H OH 2 J NH ' Η H 0X0 Cl Cl OH ₂ 1 NH Η H 0X0 Cl H OH 2 1 NH

H H 0X0 Cl H H 0X0 ch ₃ H H 0X0 CH; H H 0X0 H H H 0X0 Cl H H 0X0 Cl H H 0X0 Cl

CH; OH 2 1 NH CH; OH 1 1 NSO ₂ C ₂ H ₅ H OH 1 1 NSO ₂ C ₂ H ₅ H OH 1 1 NSO ₂ C ₂ H; Cl OH 1 1 NSO ₂ C ₂ H ₅ H OH 1 1 nso ₂ c ₂ h ₅ ch ₃ OH 1 1 NSO ₂ C ₂ H ₅

Table 8

R ³¹ R ^3t> R ¹ R ² R R ⁵ n m x H H -OCH ₂ CH ₂ 0 · ch ₃ CH; 2 1 NS0 ₂ CH ₃ H H -och ₂ ch ₂ o- ch ₃ H 2 1 nso ₂ ch ₃ H H -och ₂ ch ₂ o- H H 2 1 nso ₂ ch ₃ H H -och ₂ ch ₂ o- Cl Cl 2 1 nso ₂ ch ₃ H H -och ₂ ch ₂ o- Cl H 2 1 nso ₂ ch ₃ H H -och ₂ ch ₂ o- C) ch ₃ 2 1 nso ₂ ch ₃ H H -och ₂ ch ₂ o- N0 ₂ H 2 and nso ₂ ch ₃ H H -och ₂ ch ₂ o- ch ₃ CH; 2 .1 0 H H -och ₂ ch ₂ o- ch ₃ H 2 1 0 H H -och ₂ ch ₂ o- H H 2 1 0 H H -och ₂ ch ₂ o- Cl Cl 2 1 0 H H -och ₂ ch ₂ o- Cl H 2 1 0 H H -och ₂ ch ₂ o- Cl CH ₃ 2 1 0 CH; H -och ₂ ch ₂ o- ch ₃ CH; 2 ] NH H H -och ₂ ch ₂ o- ch ₃ H 2 1 NH H H -och ₂ ch ₂ o- H H 2 1 NH H H -och ₂ ch ₂ o- Cl Cl 2 1 NH H H -och ₂ ch ₂ o- Cl H 2 1 NH H H -och ₂ ch ₂ o- Cl CH ₃ 2 1 NH H H -OCH ₂ CH (CH ₃ ) O - ch ₃ CH; 2 1 nso ₂ ch ₃ H H -OCH ₂ CH (CH ₃ ) O - ch ₃ H 2 ] nso ₂ ch ₃ H H -OCH ₂ CH (CH ₃ ) 0 - H H 2 1 nso ₂ ch ₃

H H -OCH ₂ CH (CH 2) O - Cl Cl ³ 1 NSO ₂ CH H H -OCH ₂ CH (CH 2) O - Cl. H 2 1 nso ₂ ch H H • OCH ₂ CH (CH ₃ ) O- Cl CH; 2 1 NSCHCH

R ³²

H

H

H

H

H

H

CH;

CH;

CH;

CH;

oh

CH;

CH;

CH;

CH;

oh

CH;

CH;

H

H

H

H

H

H

CH;

CH;

Table 9

H -och ₂ ch ₂ o- CH; H -OCH ₂ CH ₂ O- H H -OCH ₂ CH ₂ O. Cl H -och ₂ ch ₂ o- Cl H -och ₂ ch ₂ o- Cl CH; -och ₂ ch ₂ o- CH; CH; -och ₂ ch ₂ o- oh CH; -och ₂ ch ₂ o- H CH; -och ₂ ch ₂ o- Cl CH; OCH-Ch-yo- - Cl CH; -och ₂ ch ₂ o- Cl H -och ₂ ch ₂ o- CH; H -och ₂ ch ₂ o- CH; H -och ₂ ch ₂ o- H H -och ₂ ch ₂ o- Cl H -och ₂ ch ₂ o- Cl H -och ₂ ch ₂ o- Cl H -och ₂ ch ₂ o- CH; H -och ₂ ch ₂ o- CH; H -och ₂ ch ₂ o- H H -och ₂ ch ₂ o- Cl H -och ₂ ch ₂ o- Cl H -och ₂ ch ₂ o- Cl CH; -och ₂ ch ₂ o- CH; CH; -och ₂ ch ₂ o- CH;

H 2 1 CH; H 2 1 CH; Cl 2 1 CH; H 2 1 CH; CH; 2 1 CH; CH; 2 1 CH; H 2 1 CH; H 2 1 CH; Cl 2 I CH; H 2 1 CH; CH; 2 1 CH; CH; 2 1 CH; H 2 1 CH; H 2 1 CH; Cl 2 1 ch ₃ H 2 1 CH; CH; 2 1 CH; CH; 2 1 CH; H 2 1 CH; H 2 1 CH ₃ Cl 2 1 CH; H 2 ’CH; CH; 2 1 CH; CH; 2 1 CH; H 2 1 CH;

R ¹¹

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

CH

CH

CH

CH

CH

CH

CH

CH

ch ₃ ch ₃ -OCH ₂ CH ₂ O · H H ₂ I ch ₃ C «3 ch ₃ CH; -OCH2CH2O- Cl Cl ₂ 1 ch ₃ CH; ^CH 3 CH; -och ₂ ch ₂ o- Cl H 1 1 ch ₃ CH; ch ₃ CH; -och ₂ ch ₂ o- ci CH ₃ n 1 CH; ch ₃ ch ₃ H -OCHiCHoO- ·. A. ch ₃ ch ₃ 2 1 ch ₃ CH; ch ₅ H -och ₂ ch ₂ o- CH; H 2 1 ch ₃ ch ₃ ch ₃ H -och ₂ ch ₂ o- H H 2 1 ch ₃ ch ₃ ch ₃ H -och ₂ ch ₂ o- Cl Cl 2 1 ch ₃ ch ₃ ch ₃ H -och ₂ ch ₂ o- Cl H 2 1 ch ₃ CH; ch ₃ H -och ₂ ch ₂ o- Cl ch ₃ 2 1 ch ₃ ch ₃ H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2. 0 ch ₃ 'H H H -och ₂ ch ₂ o- ch ₃ H 2 0 ch ₃ H H H -och ₂ ch ₂ o- H H 2 0 ch ₃ H H H -och ₂ ch ₂ o- Cl Cl 2 0 ch ₃ H H H -och ₂ ch ₂ o- Cl H 2 0 ch ₃ H H H -och ₂ ch ₂ o- Cl CH ₃ 2 0 ch ₃ H ch ₃ CH ₃ -ock ₂ ch ₂ o- ch ₃ ch ₃ 2 0 ch ₃ H ch ₃ CH; -och ₂ ch ₂ o- ch ₃ H 2 0 ch ₃ H ch ₃ CH ₃ -och ₂ ch ₂ o- H H 2 0 ch ₃ H ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl 2 0 ch ₃ H ch ₃ ch ₃ -och ₂ ch ₂ o- Cl ’H 2 0 ch ₃ H ch ₃ ch ₃ -och ₂ ch ₂ o- Cl CH ₃ 2 0 ch ₃ H ch ₃ H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 0 ch ₃ ch ₃ ch ₅ H -och ₂ ch ₂ o- ch ₃ H 2 0 ch ₃ ch ₃ «3 H -och ₂ ch ₂ o · H H 2 0 ch ₃ ch ₃ ch ₃ H -och ₂ ch ₂ o- Cl Cl 2 0 ch ₃ ch ₃ ch ₃ H -och ₂ ch ₂ o- Cl H 2 0 ch ₃ ch ₃ ch ₃ . H -och ₂ ch ₂ o- Cl ch ₃ 2 0 ch ₃ ch ₃ H H -och ₂ ch ₂ o- ch ₃ ch ₃ 2 0 ch ₃ ch ₃ H H -och ₂ ch ₂ o- ch ₃ H 2 0 ch ₃ ch ₃ H H -och ₂ ch ₂ o- Cl Cl 2 0 ch ₃ ch ₃ H H -och ₂ ch ₂ o- Cl H 2 0 ch ₃ ch ₃ H H -och ₂ ch ₂ o- Cl ch ₃ 2 0 ch ₃ ch ₃ ch ₃ ch ₃ -OCH ₂ CH ₂ O- ch ₃ ch ₃ 2 0 ch ₃ ch ₃ ch ₃ ch ₃ -och ₂ ch ₂ o- ch ₃ H 2 0 ch ₃ ch ₃ ch ₃ ch ₃ -och ₂ ch ₂ o- H H 2 0 ch ₃ ch ₃ ch ₃ ch ₃ -och ₂ ch ₂ o- Cl Cl 2 0 ch ₃ ch ₃

Formulation and use

The compounds of the invention are generally used as formulations together with an agriculturally acceptable carrier comprising at least one liquid diluent, solid diluent or surfactant. The individual components of said formulation or composition are selected to be consistent with the physical properties of the active ingredient, the mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include, but are not limited to, solutions (e.g., solutions (including emulsifiable concentrates), suspensions, emulsions (including emulsions (and / or suspoemulsions), and the like) which may be optionally concentrated into gels. Useful formulations further include solids, such as dusts, powders, granules, flights, tablets, films, and the like, which may be water dispersible (water-wettable) or water-soluble. The active ingredient may be encapsulated and further formed into a suspension or solid formulation; alternatively, the entire active ingredient formulation may be encapsulated (or

The encapsulation can be controlled (or with a certain coating). release of the active ingredient. Sprayable formulations may be distributed in a suitable medium and used in spray volumes ranging from about one to several hundred liters per hectare. Very strong compositions are used primarily as intermediates for further formulations.

The formulations will generally be substances, diluent and surfactant amounts, the amounts containing an effective amount of an effective amount of the active ingredient. c h of individual components always represent 100 percent in individual cases.

Materials. n o s t e r c e n t o

C onnectio n: L d I. o component

Surfactant

Water-dispersible and water-soluble granules, tablets and powders 5-90 0-94 1-15 Suspensions, emulsions, solutions C including emulsifiable k on c entrats) 5-50 40-95 0-15 dusts 1-25 70-99 0-5 Granules and pellets 0, 01-99 5-99, 99 0-15 Very strong compositions 90-99 0-10 0-2

Typical solid diluents are described in Uatkins et al., Handhook of Insecticide Dust Diluents and Carriers, 2nd ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in llardsen, Solvents Guide, 2nd ed., Interselence, New York, 1959. lcCutcheon's Deterqents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and

Wood, Encyclopedia of Surface Active Agents, Chemical Publ. What. Inc. New York, 1964, lists surfactants and their recommended uses. All formulations may contain, at least a number of suds reducing additives, sintering, cobalt, microcrystalline growth, and so forth. viscosity.

Surfactants include, for example, polyethoxylated and 3-cyano, polyoxyethylene, and 3-phenoxy, polyoxyethylene sorbitan and fatty acids, dialkyl sulfosuccinates.

a 3. k y 3. s u Ifá t y, a 1 k y 3. b e n z e n f u n t a t, a r g a n o d i 3. d. ions, N, H-diastyls 3.-taurates, 1-ignansulfonates, l-ondenzynaphthalenesulfonate 3. polyphthaldehyde, polycarboxylate and block copolymers of polyoxyethylene and polyoxypropylene . Solid diluents include, for example, clays, especially berrtonite, montmorillonite, attapulglt and kaolin,

100 starch, sugar, gluten, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate, sodium bicarbonate and sodium sulfate. Liquid diluents include, for example, water, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N, N and N. yko 1, polypropylene 1 yko 1, paraffins, alkynyl benzenes, alkylnaphthalenes, olive oil, castor oil, rope oil, tung oil, sesame oil, corn oil, coconut oil, cottonseed oil, soybean oil, rapeseed oil and peanut oil, fatty acid esters, ketones such as cylclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.

Solutions, including emulsifiable concentrates, can be prepared by simply mixing the individual ingredients. Dusts and powders can be prepared by mixing and usually grinding, for example in a hammer mill or a liquid energy mill. Suspensions are usually prepared by wet milling, see, for example, U.S. Patent 3,060,084. Granules and pellets can be prepared by spraying the active material onto preformed granule carriers or by agglomeration techniques, see, for example, Brouning Agglomeration, Chemical Engineering, December 4, 1967, p. 147-48, Perry's Chemical Engineer's Handbook, 4th ed., Grau-Hill, New York, 1963, p. 8 to 57 et seq. And WO 91/13546. Pellets can be prepared by the methods described in US 4,172,714. Water-dispersible and water-soluble granules can be prepared, for example, by the method disclosed in the US patent

4,144,050, US 3,920,442 and DE 3,246,493. For example, tablets may be prepared as described in US 5,180,587, US 5,232,701 and US 5,208,030. Films can be prepared as described, for example, in GB 2, 095, 558 and US 3,299,566.

Further information can be found, for example, in US 3,235,361, paragraph 6, line 16 through paragraph 7, line 19, and examples 10 to 41; US 3, 309, 192, paragraph 5, line 43 to paragraph 7, line 62 and examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, ' 167 and 169-182; For S 2, 891, 855, paragraph 3, line

101 to paragraph 5, line 17 and Examples 1 to. 4; Klingman, L. Feec / Control and Science, John Uiley and Sons, Inc., New York, 1961, p. 61 to 96; and Kance et al., deed Control Handhook, 8th ed., Blackwell Scientific Publications, Oxford, 1989.

In the following examples, all percentages are by weight and all formulations are prepared by conventional means. C i s 1 and z 1 e n i n i n i n i n i n i n i n d e x n e x t Tables A to C.

Example A

Very strong concentrate

Compound 2

A e r o g e 1 s i 1 d. k y

Synthetic amorphous fine silica

98.5% 0.5% 1.0%

Example B

Wettable powder

Compound 8

A d d e c tio n e n e n e n e n e n y l g g y y o l t e r L. d. g n u 1 f t K K K K K K K K em 1 ont ont ont ont ont mor ont mor ont mor mor mor mor mor))))))

65.0% 2, 0% 4, 0% 6, 0% 23, 0%

granules

Example C

Compound 2

Attapulgite granules Low melting substance 0.71 / 0.30 nm; O.S.S. no. 25-50 sieves)

0, 0% 90, 0%

102

Example D

I- x t r u d o v a n pellet

Compound 8

Anhydrous sodium sulphate

S r v 1 g g 1 1 f A A A 11 11 A11 <y 1 n f a a a i B B B B e e e e e e e e 11 11 11 11 11

0, 0% 10, 0% 5, 0% 1, 0% 59, 0%

The test results indicate that the compounds of the invention are highly active pre-emergence and post-emergence herbicides or plant growth regulators. Many of them find use in broad-spectrum pre- and post-emergence weed control in areas where complete control of all vegetation is desirable, such as around storage bins, industrial storage areas, car parks, car parks, airport areas, river banks, navigations, around billows and around roads and highways. Some compounds are useful for selective grass control and broadleaf weeds and are harmless to important agricultural crops including, for example, alpha grass, barley, cotton, wheat, rape, sugar beet, corn, sorghum soybeans, rice, oats, peanuts, vegetables, tomato, perennial (multiannual) plantation crops including coffee, cocoa, oil palm, rubber tree, citrus sugar, grapefruit, fruit trees, nuts, pisang, pineapple, teapot and forests, for example to them. era and grass species (eg blue grass

Kentucky, grass Augustine and Bermuda grass). Those skilled in the art will recognize that not all compounds are equally effective against all seeds. Alternatively, these compounds may be used for the microbiotic treatment.

reed, banana tree, eucalyptus

The compounds of the invention may be combined with other commercial herbicidal herbicide combinations

For the purpose of the commercial invention, it is possible to use the insecticides alone or with the insecticides, or they can also be used in the form of the insecticides,

103, such as benoxacor, dichloride and furilazole, which enhance the protection of certain crops. For weed control, a mixture of a compound of the invention may be used with one or more herbicides selected from the group consisting of: acetochlor, aclfluorophene, and its sodium salt, aclonlfen, acrolein C2-propenal), alachlor, ametryn, ainidosulfurone, amitrole, sulfamate, anilofos , asulam, atrazine, azimsulfuron, benazoline, benazolin-ethyl, benfurate, benfuresate, bensu fur-n-methyl, bensu id, bentazine, blfenox, bromacil, bromoxynil, bromoxynil acetate, butachlor.

b u t r a 1 in, b u t 1 a t, c h 1 o m e t o x y f, c h 1 o r a m b e, c h 1 o r b u m uron, c h 1 o r a. d a z n n, c h 1 i u m n o - e 1 1 1,, 1, c h 1 r n n 3. o,,, c c c c 3. 3. 3. 3. 3. 3. 3. 3. methyl 1, c 1 no suf 1 uron, e 1 ethod im, c 1 omazone, c 1 opyra 1 id, c 1 opyra 1 id - olamine, cycloate, cyclosulfamuron, 2, 4-D and its butyl, isopropyl esters and their dimethylammonium esters, triolamine, daimuron, dalapone, dalapon-sodium, dazomet, its dimethylammonium salt, sodium and potassium;

, butyl, isoctyl a , salts diolamine and dazomet. 2,4-DB and sol, d e smedipham.

desmetryne, dicamba and its diglycolammonium salt, dimethylammonium, sodium and potassium salts, dichlobenil, dichlorprop, diclofop-methyl, 2- (4,5-dihadro-4-methyl-4- (1-methylethyl) -5-oxo-1H) imidazol-2-yl-5-methyl-3-pyridinecarboxylic acid (AC 263, 222), difenzoquyt methilsulfate, diflufenican, dimepiperate, dimethenamide, dimethylarzinic acid and their sodium salt, dlnitramine, diphenamide, dlquat dib omid, dithiopyr, dluron, OMOC , endothal, EPTC et al a 1 f 1 uraine, eth am et 1 furo nmethyl, ethof um e, 2-dichloro-5 · 14-C-difluoromethyl) -4,5-dihydro-3- methyl-5

(1,2,4-trlazol-1-yl) -4- (fluorobenzene propanoate (F8426), ethyl, fenuron, fenuron-TCA, flamprpop-1 * 1-isopropyl).

, es p r charm b, s and t, e t y _L

-oxo-1'-phenoxypropf-1-amprpop-1'-methyl-f-azase 3. furfluf-uazifop-butyl, f-uazifop-P-butyl, f-1-urea-in, f-um-etsu 3. am, f 3 umic 1-orac-penyl, fumioxa-zi, f-uometuron, f-fluorogycophen-ethyl, f-upox am, f-uron, f-uro-1: i. don, f 1 uroxypy 1, f ^: om esafen, fosamine - ammonium, g 3. ufosinate, g 1 ufosinate - ammonium, g 1 y P hosat, g 3. yphosate - isopropy 1 ammonium, g 1 yphosate - sesquisod 1 µm, g 3. yphosate-trimesium, halosulfuron-methyl, haloxyfop-ethyl, haloxyfop-methyl, hexazirion, imazamethabenz-methyl, imazamox (AC 299 263), imazapyr, imazaquin, imazaquin-ammonium, imazethapyr10, imazethapyr4

ammonium, imazosulfuron, ioxyriil, ioxynil acetate, ioxynil-sodium, isoproturon, isoturors, isoxaben, isoxaf lutol C RPA

201772), lactofen, lenacil, linuron, maleic hydrazide, lCPA and its dimethylammonium salt, sodium and potassium salts, ľIPCA-isoctyl, mecoprop, mecoprop-P, mefenacet, mef 1 u 1 d 1 d, τη etam-sodium um, metabenz 11 azuro, methyl 1 E 2 - chloro - 4 - fluoro - 5 - CC te: trahydro - 3 - oxo -1/7, 3/7 - 1, 1, 3, 4] thiadiazole (3, 4-a] pyridazin-1-ylidene) amino] phenylthioacetate (CKIH 9201), methylarzonic acid and its calcium, mono-ammonium, monosodium and disodium salts, methyl LĽC Ľ 1 - C 5 - E 2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidene] amino] oxy] acetate (AKH-7088), methyl 5-E '(E, 4,6-dimethyl-2-pyrimidine) nyl) amino] -amino] sulfonyl] -1-C2-pyrrolidinyl-1H-pyrazole-4-carboxylate (MC-330), metobenzuron, metolachlor, metosulam, methoxuron, metribuzin, metsulfuron-methyl, molinate , monolinuron, napropamide, naptalam, neburon, nicosulfuron, norflurazone, oryzalin, oxadlazone, 3- oxetariyl

2-EEECC 4,6-Dimethyl-2-pyrimidinyl) amino-1-carbonyl] amino-1-sulfonyl-benzoate (CGA 277476), oxyfluorophene, paraquat dichlorld, pebulat, pendimethall, per fluidone, phenmedlphan, pleloram, picloram-potassium, pretilamulfur prl, protilamblur prl methyl, prometone.

prometryn, propachlor, propanil, propaquizafop, propazine, propham, propyzamide, prosulfuron, pyrazolyl, pyrazosulfuron-ethyl, pyridate, pyrithiobac, pyrithiobac-sodium, quinclorac, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-ethyl.

rimsulfuron, sethoxydim, siduron, simazine, sulcotrione (ICIA0051), sulfentrazone, sulfometuron-methyl, TCA, TCA-sodium, tebutbiuron, terbacil, terbutylazine, terbutryn, thenylchloride, thiafluamide, thifluoromethoxy, thifluoromethoxy, trifene, trifene, trifene, trifene -allat, triasulfuron, tribenuron-methyl, triclopyr, triclopyr-butyl, triclopyr-triethylainonium, tridlphan, trifluralin, triflusulfuron-methyl and vernolat.

In certain cases, combinations with other herbicides having a similar spectrum of control but a different mode of action will be very advantageous to protect against the development of resistant weeds.

Advantageous for better control of undesirable vegetation (eg using a lower dose, a wider range of weeds controlled or

In addition, the compound of the present invention is mixed with a herbicide selected from the group consisting of:. cyanazine, imazethapyr and its imazethapyr ammonium salt, nicosulfuron, primisulfuron-methyl, pyrazosulfuron-ethyl and rimsulfuron. Highly preferred mixtures of C compound numbers refer to compounds in index tables A to C) are selected from the group consisting of: compound 1 and anthrazine; compound compound 7 and imazethapyr;

and cyanazine; compound 1 and imazethapyr; compound 1 and nicosulfuron; compound 1 and primisulfuron-methyl; compound 1 and pyrazosulfuron-ethyl; compound 1 and rimsulfuron; compound 2 and atrazine; compound 2 and cyanazine; compound 2 and imazethapyr; compound 2 and nicosulfuron; compound 2 and primisulfuron-methyl, compound 2 and pyrazosulfuron-ethyl; compound 2 and rimsulfuron; and atrazine; from 1 account: i. n for compound 7a and primisulfuron-methyl, compound 7 and rimsulfuron; compound 8 and atrazine; compound 8 and cyanazine; compound 8 and imazethapyr; compound 8 and nicosulfuron; compound 8 and primisulfuron-methyl, compound 8 and pyrazosulfuron-ethyl; compound 8 and rimsulfuron; compound 10 and cyanazine; compound 7 nicosulfuron; compound 7 7 and pyrazosulfuron-ethyl;

and atrazine; compound 10 and cyanazine; compound 10 and imazethapyr; compound 10 and nicosulfuron; compound 10 and primisulfuron-methyl, compound 10 and pyrazosulfuron-ethyl; compound 10 and rimsulfuron.

The herbicidally effective amounts of the compounds of the invention are determined on the basis of many factors. These factors include: the formulation chosen, the method of application, the amount and type of vegetation present, growth conditions, etc. Usually the herbicidal amount of the compounds according to the invention is in the range of 0.001 to 20 kg / ha and preferably in the range of 0.004 to 1.0 kg / ha. Those skilled in the art can readily determine the herbicidally effective amount necessary for the desired level of weed control.

The following tests demonstrate the control efficacy of the compounds of the invention against specific weeds. However, weed control achieved by these compounds is limited to these species. See Tables A to C for a description of the compounds. The abbreviation dec | · · »indicates a compound that has decomposed upon melting. Abbreviation Pr. indicates an example and the number following this abbreviation indicates in which example the compound was prepared.

INDEX TABLE

Formula I wherein O is 0-1, X is SCO)

Y until denote CH-, k means 0 and x means . 1 Bile. R ³ · ⁷ ' R 3 S R ¹ R ^Ä R ⁴ R ⁵ R n m t. t. C C) s CPr. 1) H H -OCH ^ Chao H H OH 2 1 131 C dec) 2 CPr. 5) H H -OCH _and CH ₂ O ch ₃ ch ₃ OH 2 Third 130 C dec) 3 H H -OCHaCHCCH ₃ ) 0- ch ₃ CH _S OH 2 1 159- • 160 4 CPr. 3) H H -0CH ₂ CH _with 0 Cl Cl OH 2 1 140 C dec) 5 H H 0X0 H H OH 2 1 168 C dec) 6 ^a CPr. 6) H H -SCH-.CH-.S ch ₃ ch ₃ OH D 1 217- 222

The compound contains about 16 wt. % 2,3-dihydro-5,8-dimethylspiro [4,7-l-benzothiopyran-4,2'-Cl, 3) dithiolan] -6-carboxylic acid.

INDEX TABLE B ti r2 R ⁴

ABOUT

N - CH ₂ CH ₃

107

Formula (I) wherein t) is 0-2, X is SCO) and k is 0

Bile. R ^3e> R a, R ^{1 *} R * R ⁴ R ^s R ^Á n m 1.1. C C) 7 CPr. 2) H H ^ -OCH CH O- I-I H H 2 1 oil * 8 CPr. 4) I-I I-I -OCH _Ä CH _Ä O- ci-i ₃ 0K.- ₃ l-l 2 1 111 Cdec) 9 hl I-I -OCHaCHsO- Cl Cl H 2 1 130 Cdee) 10 I-I H oxo C-H C-p &apos; H 2 1 semi

* * See Index Table C for ¹ H NMR data.

INDEX TABLE C

Bile.

Ή NMR data of CCDCl ₃ solution, unless otherwise noted e)

Δ 1.46 (t, 3H), 2.7 (m, 2H), 3.7 (m, 2H), 4.1 (q, 2H)

4.2 to 4.3 (m, 4H), 7.7 to 8.0 (4H).

S 1.5 C (3 H), 2.5 C (3 H), 2.8 C (3 H), 3.3 C (2H),

3.7 (m, 2H), 4.1 (q, 2H), 7.3-7.46 (2H).

^{and 3} H NMR data are reported in ppm downstream of tetramethylsilane.

Cq) -quadruplet, Cm) -multiplet.

108

BIOLOGICAL. EXAMPLES OF THE INVENTION

TEST A

Seeds of Hordeum are / ulgare, Echinochloa crus galli, Gallium aparine, Philopecurus myosuroides, Stellaria media, Kanthium strumarium, Zea mays, Gossypium hirsutum, Bigitaria sanguinalis, Bromus tec t or um, Baria spp. Sativa ores, Sorghum bicolor, Glycine max, Beta vulgaris, Abutilon theophrasti, Triticum aestivum, Polygonum convolvulus, Avena fatua and Cyperus rotundus tubers were planted and treated pre-emergence with test chemicals formulated in a non-phytotoxic surfactant solvent composition.

At the same time, these crops and weeds were treated with test chemicals formulated in the same manner post-emergence. Plants having a height ranging from two to eight centimeters (one to four leaf stage) were selected for pre-emergence treatment. The treated and control plants were kept in the greenhouse for twelve to sixteen days. Upon expiry, all test samples were compared to control samples and evaluated visually. The response of the plants to the treatment is summarized in Table A. A scale of 0 to 10 was used for the evaluation, with 0 indicating no effect and 10 indicating complete control. A dash (-) in the answer box indicates that it was not, the result obtained.

109

TABLE AND COMPOUND TABLE AND COMPOUND

Dose 2000 g / ha 1 5 7 Dose 2000 g / ha 1 5 7 postemergence pre- Hordeum vulgare 0 0 0 Hordeum vulgare 0 0 0 Echinochloa crus-galli 8 0 9 Echinochloa crus-galli 0 0 2 Gallium aparine 6 0 8 Gallium aparine. 5 - 2 Alopecurus myosuroides 1 0 0 Alopecurus myosuroides 0 0 1 Stellariameďia 9 0 9 Stellariamedia 7 0 3 Xanthium strumarium 9 0 9 Xanthium strumarium 4 0 0 Zea mays 0 0 1 Zea mays 0 0 0 Gossypium hirsutum 9 0 9 Gossypium hirsutum 1 0 0 Digitaria sanguinalis 8 0 9 Digitaria sanguinalis 6 0 7 Bromus tectorum 0 0 0 Bromus tectorum 0 - 2 Setaria faberii 2 0 8 Setaria faberii 1 0 3 Chenopodi um album 9 0 9 . Chenopodium album 9 - 10 Ipomoea hederacea 9 0 2 Ipomoea hederacea 2 0 0 Cyperus rotundus 1 - 2 Cyperus rotundus 0 0 0 Brassica napus 9 0 9 Brassica napus 10 - 7 Oryza sativa 8 0 8 Oryza sativa 9 0 3 Sorghum bicolor 2 0 3 Sorghum bicolor 0 0 0 Glycine max 9 0 9 Glycine max 2 0 3 Beta vulgaris 10 0 10 Beta vulgaris 9 - 8 Abutilon theophrasti 9 0 9 Abutilon theophrasti 6 0 1 Triticum aestivum 0 0 0 Triticum aestivum 0 0 0 Polygonum convolvulus 7 0 7 Polygonum convolvulus 0 - 0 Avena fatua 0 0 0 Avena fatua 0 0 0

110

TABLE AND COMPOUND

400 g / ha postemergence ' 1 2 3 4 5 6 7 8 9 Hordeum vulgare 0 9 9 5 0 5 0 0 2 Echinochloa crus-galli 2 9 10 9 0 9 9 9 9 Gallium aparine 5 9 9 9 0 9 7 9 9 Alopecurus myosuroides 0 9 9 7 0 4 0 2 3 Stellariamedia 8 9 10 8 0 9 7 9 7 Xanthium strumarium 7 9 9 9 0 9 9 9 9 Zea mays 0 9 5 2 0 1 1 7 1 Gossypium hirsutum 7 10 10 10 0 9 9 9 9 Digitaria sanguinalis 3 10 9 7 0 6 9 9 3 Bromus tectorum 0 9 9 6 0 0 0 2 2 Setaria faberii 1 9 9 5 0 1 3 9 6 Chenopodium album 6 9 9 9 0 9 8 9 9 Ipomoea hederacea 7 10 10 10 0 9 2 8 6 Cyperus rotundus 0 7 9 2 0 2 0 - 1 Brassica napus 8 8 10 10 0 10 8 10 10 Oryza sativa 7 10 9 10 0 9 7 9 9 Sorghum bicolor 0 9 9 9 0 2 2 9 2 Glycine max 8 10 10 9 0 9 8 9 4 Beta vulgaris 10 10 10 10 0 10 10 10 10 Abutilon theophrasti 9 10 10 10 0 10 9 9 9 Triticum aestivum 0 10 9 8 0 3 0 6 2 Polygonum convolvulus 2 8 9 6 0 5 6 9 6 Avena fatua 0 9 9 4 0 4 0 8 3

111

TABLE AND COMPOUND

400 g / ha 1 2 3 4 5 6 7 8 9 pre- Hordeum vulgare 0 3 0 0 0 0 0 0 0 Echinochloa crus-galli 0 10 9 5 0 0 0 9 2 Gallium aparine - 9 8 5 0 4 0 7 2 Alopecurus myosuroides 0 2 2 2 0 0 0 0 0 Stellariamedia 0 8 10 4 - 7 0 8 7 Xanthium strumarium 0 6 9 6 0 2 0 0 3 Zea mays 0 0 0 0 0 0 0 0 0 Gossypium hirsutum 0 6 4 8 0 2 0 1 7 Digitaria sanguinalis 0 10 10 8 0 4 1 8 2 Bromus tectorum 0 6 1 6 0 0 .0 0 0 Setaria faberii 0 6 3 2 0 0 0 6 1 Chenopodium album 5 10 10 10 - 9 9 9 9 Ipomoea hederacea 0 7 9 6 - 1 0 2 0 Cyperus rotundus - 10 10 3 0 0 0 0 - Brassica napus 0 3 3 9 0 0 0 0 0 Oryza sativa 0 9 10 7 0 10 0 6 3 Sorghum bicolor 0 6 3 2 0 0 0 5 0 Glycine max 0 9 9 6 0 0 0 Third 0 Beta vulgaris 9 10 10 10 0 8 8 9 9 Abutilon theophrasti 0 10 10 10 0 6 0 10 0 Triticum aestivum 0 7 2 0 0 0 0 0 0 Polygonum convolvulus 0 7 9 6 - 0 0 0 3 Avena fatua 0 4 2 0 0 0 0 0 0

112

TABLE AND COMPOUND TABLE AND COMPOUND

200 g / ha 6 Dose 200g / ha 6 postemergence pre- Hordeum vulgare 5 Hordeum vulgare 0 Echinochloa 9 Echinochloa 0 crus-galli crus-galli Gallium aparine 9 Gallium aparine 2 Alopecurus 3 Alopecurus 0 myosuroides myosuroides Stellariamedia 9 Stellariamedia 4 Xanthium 9 Xanthium 3 strumarium strumarium Zea mays 1 Zea mays 0 Gossypium 9 Gossypium 0 hirsutum hirsutum Digitaria 5 Digitaria 6 sanguinalis sanguinalis Bromus tectorum 0 Bromus tectorum 0 Setaria faberii 2 Setaria faberii 0 Chenopodium 9 Chenopodium 9 album album Ipomoea 9 Ipomoea 1 hederacea hederacea Cyperus 2 Cyperus rotundus - rotundus Brassica napus 10 Brassica napus 0 Oryza sativa 9 Oryza sativa - Sorghum bicolor 2 Sorghum bicolor 0 Glycine max 8 Glycine max 0 Beta vulgaris 10 Beta vulgaris 8 Abutilon 10 Abutilon - theophrasti theophrasti Triticum 3 Triticum 0 aestivum aestivum Polygonum 5 Polygonum 0 convolvulus convolvulus Avena fatua 4 Avena fatua 0

113

TABLE AND COMPOUND ---------------------

Dose 100 g / ha 2 3 4 6 8 9 postemergence Hordeum vulgare 7 8 4 3 0 0 Echinochloa crus-galli 9 9 8 9 9 9 Gallium aparine 9 9 9 8 9 6 Alopecurus myosuroides 5 8 5 1 0 2 Stellariamedia 9 9 7 9 9 7 Xanthium strumari um 9 9 9 9 9 8 Zea mays 7 3 1 0 5 0 Gossypium hirsutum 10 10 10 9 9 9 Digitaria sanguinalis 9 9 2 3 9 2 Bromus tectorum 6 9 5 0 0 0 Setaria faberii 9 9 3 1 9 4 Chenopodium album 9 9 9 9 9 8 Ipomoea hederacea 10 10 10 9 8 1 Cyperus rotundus 7 6 2 0 6 0 Brassica napus 3 7 8 6 8 8 Oryza sativa 9 10 9 8 8 6 Sorghum bicolor 9 9 9 2 9 0 Glycine max 10 10 8 8 8 3 Beta vulgaris 10 10 10 10 10 9 Abutilon theophrasti 10 10 10 10 9 2 Triticum aestivum 8 8 6 2 2 1 Polygonum convolvulus 7 9 6 3 7 6 Avena fatua 4 6 3 2 4 2

114

TABLE

COMPOUND

Dose 100 g / ha PREEMERGENT Horde um vulgare

Echinochloa crus-galli Gallium aparine

Alopecurus myosuroides

Stellariamedia

Xanthium strumarium - Zea mays

Gossypium hirsutum

Digitaria sanguinalis - Bromus tectorum Setaria faberii

Chenopodium album

Ipomoea hederacea

Cyperus rotundus Brassica napus Sorghum bicolor Glycine max Beta vulgaris

Abutilon theophrasti

Triticum aestivum

Polygonum convolvulus - Avena fatua

3 4

0 0

8 1

8 6

0 1

8 3

3 2

0 0

4 3

9 7

0 0

1

10 9

2 5

10 0 3

8 7

0 1

9 5

10 10

9 9

0 0

2 2

0

8 9

0 0

0 0

3 0

0 0

6 7

0 0

0 0

0 0

0

0 0

4 0

9 8

0 0

0 0

2 0

0 0

0 0

9 9

5 0

0 0

0 0

0 0

115

TABLE AND COMPOUND TABLE AND COMPOUND

Dose 50 g / ha 3 6 Dose 50 g / ha 3 6 postemergence pre- Horde um vulgare 4 1 Hordeum vulgare 0 0 Echinochloa 9 9 Echinochloa 5 0 crus-galli crus-galli Gallium aparine 9 8 Gallium aparine 2 0 Alopecurus myosuroides 6 0 Alopecurus myosuroides 0 0 Stellariamedia 9 9 Stellariamedia 7 0 Xanthium 9 9 Xanthium 3 0 strumarium strumarium Zea mays 1 0 Zea mays 0 0 Gossypium hirsutum 10 9 Gossypium hirsutum 0 0 Digitaria sanguinalis 9 3 D i gitaria sanguinalis 8 1 Bromus tectorum 7 0 Bromus tectorum 0 0 Setaria faberii 8 0 Setaria faberii 2 0 Chenopodium album 9 9 Chenopodium album 10 8 Ipomoea hederacea 10 9 Ipomoea hederacea 0 0 Cyperus rotundus 6 1 Cyperus rotundus 0 0 Brassica napus 6 - Brassica napus 0 0 Oryza sativa 10 9 Oryza sativa 8 0 Sorghum bicolor 9 1 Sorghum bicolor 0 0 Glycine max 10 8 Glycine max 6 0 Beta vulgaris 10 10 Beta vulgaris 10 0 Abutilon 10 10 Abutilon 7 0 theophrasti theophrasti Triticum 8 2 Triticum 0 0 aestivum aestivum Polygonum convolvulus 8 3 Polygonum convolvulus 0. 0 Avena fatua 6 2 Avena fatua 0 0

116

TABLE COMPOUND TABLE ZLÚČFNINA. Dose 10 g / ha 3 Dose 10 g / ha 3 postemergence pre- Hordeum vulgare 2 Hordeum vulgare 0 Echinochloa crus-galli 9 Echinochloa crus-galli 0 Gallium aparine 7 Gallium aparine 0 Alopecurus myosuroides 3 Alopecurus myosuroides 0 Stellariamedia 7 Stellariamedia 0 Xanthium strumarium 9 Xanthium strumari um 1 Zea mays 0 Zea mays 0 Gossypium hirsutum 10 Gossypium hirsutum 0 Digitaria sanguinalis 8 Digitaria sanguinalis 2 Bromus tectorum 0 Bromus tectorum 0 Setaria faberii 2 Setaria faberii 0 Chenopodium album 9 Chenopodium album 10 Ipomoea hederacea 9 Ipomoea hederacea 0 Cyperus rotundus 0 Cyperus rotundus 0 Brassica napus 0 Brassica napus 0 Oryza sativa 9 Oryza sativa 1 Sorghum bicolor 3 Sorghum bicolor 0 Glycine max 7 Glycine max 2 Beta vulgaris 10 Beta vulgaris 9 Abutilon theophrasti 10 Abutilon theophrasti 2 T.riticum aestivum 2 Triticum aestivum 0 Polygonum convolvulus • 2 'Polygonum convolvulus 0 Avena fatua 1 Avena fatua 0

117

TEST B

The compounds evaluated in this test were formulated in a non-phytotoxic solvent composition that includes a surfactant and applied to the soil surface before the plants were <pre-emergence application), to the water that covered the soil surface (flood application) and to the plants which were in the stage of one to four sheets (Post-emergence application). Clay soil was used for the flood test. The water depth for the flood test was approximately 2.5 cm and was maintained throughout the test.

The plant species used in the pre-emergence and post-emergence tests were Hardeum vulgare, Echinochloa crus-galli, Gallius aparine, Nopopurus wyosuroides, Stellaria media, Xanthiumstrumarium, Zea may.s, Gossypium hirsutum, Digitaria sanguinalis, Bromus sanguinalis, Bromus sanguinalis, Bromus. se, Chenopodium album, Ipomoea hederacea, Amaranth.s retroflexus, Bra. All plant species were planted one day prior to compound administration for the pre-emergence portion of this assay. growing; These plants were controlled to obtain plants of approximately the size suitable for the pre-emergence portion of the assay. The plant species in the case of the flood test were Oryza sativa, Cyperus difformis, Heterantbera limosa, Echinochloa crus-qalli, Einochloa oryzicola, which were grown to the 2-leaf stage for test purposes.

All plant species were grown using conventional greenhouse practice. Visual: damage evaluation of the treated plants, when compared to untreated plants, was recorded approximately fourteen to twenty-one days after application of the test compound. The responses: plants to these compounds are summarized in Table B. For evaluation: a scale of 0 to ICO was used, with 0 representing no effect and 100 representing complete control. A dash (-) in the response column indicates that no result was obtained.

118

TABLE B

Dose 500 g / ha

postemergence

Hordeum vulgare

Echinochloa crus-galli

Echinochloa crus-galli

Gallium aparine

Alopecurus myosuroides

Stellaria media

Xanthium strumarium

Zea mays

Gossypium hirsutum

Digitaria sanguinalis

Bromus tectorunm

Heteranthera limosa

Setaria faberii

Lolium multiflorum

Sorghum halpense

Chenopodium album

Ipomoea hederacea

Brassica napus

Amaranthus retroflexus

Oryza sativa

Glycine max

Veronica persica

Beta vulgaris Cyperus dufformis Abutilon theophrasti Echinochloa aoryzicola Triticum aestivum Polygonum convolvulus

COMPOUND

119

TABLE B COMPOUND

Dose 500 g / ha 7

Pre-emergence

Hordeum vulgare 1

Echinochloa crus-galli

Gallium aparine 0

Alopecurus myosuroides

Stellaria media 0

Xanthium strumarium 0

Zea mays

Gossypium hirsutum 0

Digitaria sanguinalis

Bromus tectorunm 1

Setaria faberii 20

Lolium multiflorum

Sorghum halpense

Chenopodium album 95

Ipomoea hederacea

Brassica napus 0

Amaranthus retroflexus

Glycine max 0

Veronica persica

Beta vulgaris

Abutilon theophrasti

Triticum aestivum 0

Polygonum convolvulus 1

Avena fatua

120

TABLE B

Dose 250 g / ha POSTEMERGENT Hordeum vulgare Echinochloa crus-galli Echinochloa crus-galli Gallium aparine Alopecurus myosuroides Stellaria media Xanthium strumarium Zea mays

Gossypium hirsutum Digitaria sanguinalis Bromus tectorunm Heteranthera limosa Setaria faberii Lolium multiflorum Sorghum halpense Chenopodium album Ipomoea hederacea Brassica napus Amaranthus Retroflexus Oryza sativa Glycine max

Veronica persica Cyperus dufformis Abutilon theophrasti Echinochloa aoryzicola Triticum aestivum Polygonum convolvulus Avena fatua

COMPOUND (flood) 7 0

90 40 65 90 0

84 25 45 50 0

90 95 90 60 ⁹⁰ 100 100 50 100

65 0

121

TABLE B COMPOUND 250 g / ha 4 7 Pre-emergence Hordeum vulgare 0 0 Echinochloa crus-galli 95 10 Gallium aparine 80 0 Alopecurus myosuroides 0 0 Stellaria media 0 0 Xanthium strumarium 50 0 Zea mays 0 10 Gossypium hirsutum 70 0 Digitaria sanguinalis 100 80 Bromus tectorunm 0 0 Setaria faberii 85 0 Lolium multiflorum 0 0 Sorghum halpense 30 0 Chenopodium album 90 95 Ipomoea hederacea 100 0 Brassica napus 95 0 Amaranthus retroflexus - 0 Glycine max 90 0 Veronica persica 100 0 Beta vulgaris 100 0 Abutilon theophrasti 100 0 Triticum aestivum 0 0 Polygonum convolvulus 10 0 Avena fatua 0 0

122

TABLE B COMPOUND Dose 125 g / ha postemergence 2 4 7 8 Hordeum vulgare 75 0 - 0 Echinochloa crus-galli (Flood) 100 60 10 95 Echinochloa crus-galli 90 70 90 90 Gallium aparine 100 90 - 85 Alopecurus myosuroides 80 30 - 40 Stellaria media 95 65 - 100 Xanthium strumarium 90 90 85 90 Zea mays 0 0 0 35 Gossypium hirsutum 100 90 30 95 Digitaria sanguinalis 90 75 80 90 Bromus tectorunm 60 20 - 0 Heteranthera limosa 35 30 15 35 Setaria faberii 90 40 40 90 Lolium multiflorum 70 0 - 0 Sorghum halpense 90 - 20 90 Chenopodium album 100 95 - 100 Ipomoea hederacea ¹ 90 90 50 90 Brassica napus 70 95 - 90 Amaranthus retroflexus 90 90 70 95 Oryza sativa 95 40 30 70 Glycine max 90 80 70 90 Veronica persica 100 95 - 100 Beta vulgaris 100 100 - 100 Cyperus dufformis 75 40 0 85 Abutilon theophrasti 95 100 85 100 Echinochloa aoryzicola 95 65 0 80 Triticum aestivum 75 0 - 0 Polygonum convolvulus 70 65 - 70 Avena fatua 50 0 - 65

123

TABLE B COMPOUND Dose 125 g / ha 2 4 7 8 Pre-emergence Hordeum vulgare 0 0 0 0 Echinochloa crus-galli 95 50 10 100 Gallium aparine 95 65 0 0 Alopecurus myosuroides 10 0 0 0 Stellaria media 100 0 0 95 Xanthium strumarium 70 40 0 30 Zea mays 0 0 0 20 Gossypium hirsutum 90 40 0 20 Digitaria sanguinalis 100 90 40 100 Bromus tectorunm 10 - 0 0 Setaria faberii 50 40 0 100 Lolium multiflorum 40 0 0 0 Sorghum halpense 35 20 0 20 Chenopodium album 100 90 90 100 Ipomoea hederacea 85 75 0 50 Brassica napus 0 30 0 0 Amaranthus retroflexus 90 - 0 100 Glycine max 90 70 0 20 Veronica persica 100 90 0 100 Beta vulgaris 100 100 0 100 Abutilon theophrasti 100 100 0 100 Triticum aestivum 0 0 0 0 Polygonum convolvulus 10 0 0 0 Avena fatua 0 0 0 0

124

TABLE B COMPOUND Dose 62 g / ha 2 3 4 7 8 9 POSTEľlERGENTNÁ Hordeum vulgare 65 0 10 - 0 0 Echinochloa crus-galli 95 85 35 0 95 0 Echinochloa crus-galli 90 90 55 80 90 70 Gallium aparine 80 95 90 - 80 45 Alopecurus myosuroides 80 55 30 - 35 0 Stellaria media 95 85 65 - 100 60 Xanthium strumarium 90 90 90 70 90 70 Zea mays 0 0 30 0 0 10 Gossypium hirsutum 90 90 100 20 95 30 Digitaria sanguinalis 90 90 75 50 90 30 Bromus tectorunm 50 10 25 - 0 0 Heteranthera limosa 25 15 15 0 35 0 Setaria faberii 90 80 30 10 90 50 Lolium multiflorum 50 10 0 - 0 0 Sorghum halpense 90 - 55 20 90 10th Chenopodium album 100 100 100 - 100 95 Ipomoea hederacea 90 90 90 20 90 80 Brassica napus 40 65 90 - 90 60 Amaranthus retroflexus 80 90 90 60 95 80 Oryza sativa 90 50 25 25 50 0 Glycine max 90 90 90 50 85 40 Veronica persica 95 100 95 - 100 60 Beta vulgaris 100 100 100 - 100 100 Cyperus dufformis 65 40 15 0 60 0 Abutilon theophrasti 95 100 100 70 100 60 Echinochloa aoryzicola 95 80 20 0 65 0 Triticum aestivum 70 50 30 - 0 0 Polygonum convolvulus 50 65 45 - 70 20 Avena fatua 40 0 0 - 45 0

125

TABLE B

COMPOUND

Dose 62 g / ha PREEľlERGENTNÁ 2 3 4 7 8 9 Hordeum vulgare 0 0 0 0 0 0 Echinochloa crus-galli 85 90 20 0 70 0 Gallium aparine 50 70 10 0 0 0 Alopecurus myosuroides 0 0 0 0 0 0 Stellaria media 100 85 0 0 75 0 Xanthium strumarium 50 70 20 0 20 10 Zea mays 0 25 0 0 10 0 Gossypium hirsutum 90 50 30 0 - 0 Digitaria sanguinalis 100 100 50 20 40 0 Bromus tectorunm 0 80 0 0 0 0 Setaria faberii 40 40 20 0 80 0 Lolium multiflorum 0 10 0 0 0 0 Sorghum halpense 25 70 10 0 10 - Chenopodium album 100 100 95 0 95 95 Ipomoea hederacea 60 0 65 0 0 0 Brassica napus 0 0 0 0 0 0 Amaranthus retroflexus 10 - 75 0 70 30 Glycine max 80 40 40 0 0 10 Veronica persica 95 100 95 0 100 - Beta vulgaris 100 100 100 0 100 85 Abutilon theophrasti 100 100 100 0 60 10 Triticum aestivum 0 0 0 0 0 0 Polygonum convolvulus 0 0 0 0 0 0 Avena fatua 0 20 0 0 0 0

126

TABLE B

COMPOUND

Dose 31 g / ha postemergence 2 3 4 8 9 Horde um vulgare 35 0 10 0 0 Echinochloa crus-galli 85 85 20 80 0 Echinochloa crus-galli 90 90 40 90 50 Gallium aparine 80 85 80 80 0 Alopecurus myosuroides 40 30 30 25 0 Stellaria media 80 85 60 100 50 Xanthium strumarium 80 90 90 90 70 Zea mays 0 0 0 0 0 Gossypium hirsutum 90 90 90 95 30 Digitaria sanguinalis 90 90 60 90 20 Bromus tectorunm 20 0 10 0 0 Heteranthera limosa 20 15 0 0 0 Setaria faberii 90 50 20 90 30 Lolium multiflorum 40 10 0 0 0 Sorghum halpense 70 - 45 85 10 Chenopodium album 95 100 95 100 95 Ipomoea hederacea 90 90 90 90 80 Brassica napus 30 20 90 70 35 Amaranthus retroflexus 70 90 80 95 60 Oryza sativa 65 35 25 30 0 Glycine max 90 90 90 75 30 Veronica persica 70 95 80 100 15 Beta vulgaris 100 100 100 100 90 Cyperus dufformis 30 25 0 20 0 Abutilon theophrasti 95  100 95 100 50 Echinochloa aoryzicola 80 30 0 25 0 Triticum aestivum 55 35 25 0 0 Polygonum convolvulus 50 35 30 50 20 Avena fatua 20 0 0 20 0

127

TABLE B 3 COMPOUND Dose 31 g / ha Pre-emergence 2 4 8 9 Hordeum vulgare 0 0 0 10 0 Echinochloa crus-galli 50 30 0 50 0 Gallium aparine 0 20 10 80 0 Alopecurus myosuroides 0 0 0 0 0 Stellaria media 0 70 0 55 0 Xanthium strumarium 40 50 10 0 10 Zea mays 0 0 0 0 0 Gossypium hirsutum 10 50 10 0 0 Digitaria sanguinalis 100 80 20 70 0 Bromus tectorunm 0 40 0 0 0 Setaria faberii 20 - 35 70 0 Lolium multiflorum 0 0 0 40 0 Sorghum halpense 10 50 0 70 - Chenopodium album 95 95 95 90 30 Ipomoea hederacea 50 0 20 100 0 Brassica napus 0 0 0 95 0 Amaranthus retroflexus 10 - 20 0 20 Glycine max 55 - 20 40 10 Veronica persica 30 100 95 100 100 Beta vulgaris 100 100 100 40 80 Abutilon theophrasti 100 80 30 30 0 Triticum aestivum 0 0 0 0 0 Polygonum convolvulus. 0 0 0 20 0 Avena fatua 0 0 0 0 0

128

TABLE B

Dose 16 g / ha

POSTEMERGENT Hordeum vulgare Echinochloa crus-galli Echinochloa crus-galli Gallium aparine Alopecurus myosuroides Stellaria media

Gossypium hirsutum Digitaria sanguinalis Bromus tectorunm Heteranthera limosa Setaria faberii Lolium multiflorum Sorghum halpense Chenopodium album Ipomoea hederacea Brassica napus Amaranthus Retroflexus Oryza sativa Glycine max

Veronica persica Cyperus dufformis Abutilon theophrasti Echinochloa aoryzicola Triticum aestivum Polygonum convolvulus Avena fatua

2 COMPOUND 3 4 8 9 0 0 10 0 0 (Flood) 20 40 0 65 0

90 90 20 90 20 70 85 40 65 0 20 15 10 5 0 70 85 10 100 10 80 90 90 90 50 0 0 0 0 0 90 90 90 95 20 85 90 40 90 10 10 0 0 0 0 0 0 0 0 0 70 40 10 95 10 10 10 0 0 0 60 - 35 65 0 95 95 90 100 90 90 90 90 95 40 20 15 70 35 20 50 90 60 100 30 30 25 0 20 0 90 80 80 75 30 70 90 40 100 0 100 100 100 100 80 30 0 0 0 0 95 100 90 100 30 0 15 0 15 0 40 0 0 0 0 30 35 20 45 10 10 0 0 10 0

129

TABLE B

COMPOUND

Dose 16 g / ha 2 3 4 8 9 Pre-emergence Hordeum vulgare 0 0 0 0 0 Echinochloa crus-galli 35 20 0 15 0 Gallium aparine 0 10 0 80 0 Alopecurus myosuroides 0 0 0 0 0 Stellaria media 0 50 0 25 0 Xanthium strumarium 30 30 0 0 10 Zea mays 0 0 0 0 0 Gossypium hirsutum 10 30 0 0 0 Digitaria sanguinalis 95 - 0 5 0 Bromus tectorunm 0 0 0 0 0 Setaria faberii 0 40 0 20 0 Lolium multiflorum 0 0 0 25 0 Sorghum halpense 10 50 0 40 - Chenopodium album 95 90 95 55 30 Ipomoea hederacea 50 0 0 60 0 Brassica napus 0 0 0 50th 0 Amaranthus retroflexus 0 - 0 0 0 Glycine max 20 - 10 30 0 Veronica persica 30 100 0 100 100 Beta vulgaris 80 100 100 30 0 Abutilon theophrasti 100 50 0 50 0 Triticum aestivum 0 0 0 0 0 Polygonum convolvulus 0 0 0 20 0 Avena fatua 0 0 0 0 0

130

TABLE B COMPOUND Dose 8 g / ha postemergence 3 4 8 9 Hordeum vulgare 0 10 0 0 Echinochloa crus-galli 25 0 - 0 Echinochloa crus-galli 90 15 90 10 Gallium aparine 80 20 50 0 Alopecurus myosuroides 10 0 0 0 Stellaria media 85 0 95 0 Xanthium strumarium 90 80 90 35 Zea mays 0 0 0 0 Gossypium hirsutum 80 80 90 20 Digitaria sanguinalis 90 30 80 0 Bromus tectorunm 0 0 0 0 Heteranthera limosa 0 0 - 0 Setaria faberii 30 0 85 0 Lolium multiflorum 0 0 0 0 Sorghum halpense - 20 40 0 Chenopodium album 95 80 95 85 Ipomoea hederacea 90 90 90 40 Brassica napus 15 50 0 0 Amaranthus retroflexus 90 20 85 20 Oryza sativa 20 0 - 0 Glycine max 80 70 70 20 Veronica persica 80 10 80 0 Beta vulgaris 100 100 100 10 Cyperus dufformis 0 0 - 0 Abutilon theophrasti 90 90 100 30 Echinochloa aoryzicola 15 0 - 0 Triticum aestivum 0 0 0 0 Polygonum convolvulus 35 0 40 0 Avena fatua 0 0 0 0

131

TABLE B

Dose 8 g / ha

Pre-emergence

Horde um vulgare Echinochloa crus-galli Gallium aparine Nopecurus myosuroides Stellaria media Xanthium strumarium Zea mays

Gossypium hirsutum Digitaria sanguinalis Bromus tectorunm Setaria faberii Lolium multiflorum Sorghum halpense Chenopodium album Ipomoea hederacea Brassica napus Amaranthus retroflexus Glycine max

Veronica persica Beta vulgaris Triticum aestivum Polygonum convolvulus Avena fatua

ABOUT

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ABOUT

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ABOUT

COMPOUND

8 9

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ABOUT

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100

ABOUT

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100

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100 o

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'132

TABLE B COMPOUND 4 g / ha 4 8 9 postemergence Hordeum vulgare 10 0 0 Echinochloa crus-galli 0 - 0 Echinochloa crus-galli 0 90 0 Gallium aparine 20 35 0 Alopecurus myosuroides 0 0 0 Stellaria media 0 80 0 Xanthium strumarium 65 80 10 Zea mays 0 0 0 Gossypium hirsutum 10 90 0 Digitaria sanguinalis 10 70 0 Bromus tectorunm 0 0 0 Heteranthera limosa 0 - 0 Setaria faberii 0 60 0 Lolium multiflorum 0 0 0 Sorghum halpense 10 30 0 Chenopodium album 80 80 80 Ipomoea hederacea 40 80 30 Brassica napus 10 0 0 Amaranthus retroflexus 10 70 10 Oryza sativa 0 - 0 Glycine max 50 70 10 Veronica persica 0 70 0 Beta vulgaris 100 100 10 Cyperus dufformis 0 - 0 Abutilon theophrasti 90 100 20 Echinochloa aoryzicola 0 - 0 Triticum aestivum 0 0 0 Polygonum convolvulus 0 40 0 Avena fatua 0 0 0

133

TABLE B COMPOUND 4 g / ha 4 8 9 PREENERGENTNÁ Hordeum vulgare 0 0 0 Echinochloa crus-galli 0 0 0 Gallium aparine 0 0 0 Alopecurus myosuroides 0 0 0 Stellaria media 0 0 0 Xanthium strumarium 0 0 0 Zea mays 0 0 0 Gossypium hirsutum 0 0 0 Digitaria sanguinalis 0 0 0 Bromus tectorunm 0 0 0 Setaria faberii 0 0 0 Lolium multiflorum 0 0 0 Sorghum halpense 0 30 - Chenopodium album 0 90 0 Ipomoea hederacea 0 20 0 Brassica napus 0 0 0 Amaranthus retroflexus 0 - 0 Glycine max 0 10 0 Veronica persica 0 90 10 Beta vulgaris 0 0 0 Abutilon theophrasti 0 0 0 Triticum aestivum 0 0 0 Polygonum convolvulus 0 0 0 Avena fatua 0 0 0

134

TABLE B

Dose 2 g / ha

POSTEMERGENT Hordeum vulgare Echinochloa crus-galli Echinochloa crus-galli Gallium aparine Alopecurus myosuroides Stellaria media

Gossypium hirsutum Digitaria sanguinalis Heteranthera limosa Setaria faberii Lolium multiflorum Sorghum halpense Chenopodium album Ipomoea hederacea Brassica napus Amaranthus retroflexus Oryza sativa

Glycine max

Veronica persica Cyperus dufformis Abutilon theophrasti Echinochloa aoryzicola Triticum aestivum Polygonum convolvulus Avena fatua

COMPOUND (flood)

100

135

TABLE B COMPOUND

Dose 2 g / ha 8

Pre-emergence

Hordeum vulgare O

Echinochloa crus - galli O

Gallium aparine O

Alopecurus myosuroides

Stellaria Media O

Xanthium strumarium

Zea mays O

Gossypium hirsutum 0

Digitaria sanguinalis O

Bromus tectorunm O

Setaria faberii O

Lolium multiflorum

Sorghum halpense

Chenopodium album 70

Ipomoea hederacea O

Brassica napus

Amaranthus retroflexus

Glycine max

Veronica persica

Beta vulgaris

Abutilon theophrasti

Triticum aestivum O

Polygonum convolvulus O

Avena fatua O

136

TABLE B

Dose 1 g / ha

postemergence

Hordeum vulgare

Echinochloa crus-galli

Echinochloa crus-galli

Gallium aparine

Alopecurus myosuroides

Stellaria media

Xanthium strumarium

Zea mays

Gossypium hirsutum

Digitaria sanguinalis

Bromus tectorunm

Heteranthera. limosa

Setaria faberii

Lolium multiflorum

Sorghum halpense

Chenopodium album

Ipomoea hederacea

Brassica napus

Amaranthus retroflexus

Oryza sativa

Glycine max

Veronica persica

Beta vulgaris

Cyperus dufformis

Abutilon theophrasti

Echinochloa aoryzicola

Triticum aestivum

Polygonum convolvulus

Avena fatua

COMPOUND

137

TABLE B COMPOUND Dose 1 g / ha 8 PREEľlERGENTNÁ Hordeum vulgare 0 Echinochloa crus-galli 0 Gallium aparine 0 Alopecurus myosuroides 0 Stellaria media 0 Xanthium strumarium 0 Zea mays 0 Gossypium hirsutum 0 Digitaria sanguinalis 0 Bromus tectorunm 0 Setaria faberii 0 Lolium multiflorum 0 Sorghum halpense 0 Chenopodium album 40 Ipomoea hederacea 0 Brassica napus 0 Amaranthus retroflexus - Glycine max 0 Veronica persica 0 Beta vulgaris 0 Abutilon theophrasti 0 Triticum aestivum 0 Polygonum convolvulus 0 Avena fatua 0

138

TESt C

Seeds of Echinochloa crus-galli, Convolvulus arvensis, Solanum ptycanthum dunal. Cassia obtusifolium, Xanthium strumarium, Ambrosia artemisiifolea, Zea mays, Gossypium hirsutum, Digitaria species, Panicum dichotomiflorum, Setaria faberii, Setaria viridis, Sorghum halepense, Chenopodium album, Ssp. Retrofosia, Amaranth species, platyphylla, Polygonum pensih / anicum, Glycine max, Helicanthus anriuus, Abutilon theophrasti, Panicum miliacertum,

Eríochloa villosa, Setaria lutescens and Cyperus rotundus have been planted on clayey soil. These crops and weeds were grown in the greenhouse until they reached a height of two to eight centimeters (one to four leaf stage), then treated post-emergence with test compounds formulated in a non-toxic solvent mixture containing a surfactant. Plants that were pre-emergence treated were planted immediately prior to application of the test chemical. The florets treated in this way were placed in a greenhouse and maintained under normal greenhouse conditions.

plants and untreated control plants were left at about 14 to about 14 ° C. 21 days after application of the tested response evaluation; a plant that is; summarized in and used a scale of 0 to 100 in which 0 stands for and 100 stands for complete control.

Saved in greenhouse p compounds. On Table C, with no effect

139

TABLE C COMPOUND

Dose 70 g / ha 2

POSTEľlERGENTNÁ

Echinocloa crus-galli

Convolvulus arvensis 100

Solanum ptycanthum dunal 100

Cassia obtusifolia

Xanthium strumarium 100

Zea mays

Gossypium hirsutum 100 species Digitaria 100

Panicum dichotomiflorum 100

Setaria faberii 90

Setaria viridis

Datura stramonium 100

Sorghum halepense

Chenopodium album 100 species Ipomoea 100

Cyperus rotundus 90

Amaranthus retroflexus 100

Sida spinosa 100

Ambrosia artemisiifolia 100

Sorghum vulgare 100

Brachiaria platyphylla 100

Polygonum pensilvanicum 100

Glycine max 100

Helianthus annuus

Abutilon theoprasti 100

Panicum miliacenum 100

Eriochloa villosa

Setaria lutescens

140

TABLE U COMPOUND Dose 35 g / ha 2 8 postemergence Echinocloa crus-galli 100 90 Convolvulus arvensis 100 50 Solanum ptycanthum dunal 100 100 Cassia obtusifolia - 10 Xanthium strumarium 100 90 Zea mays 5 0 Gossypium hirsutum 100 40 species Digitaria 90 70 Panicum dichotómiílorum 100 90 Setaria faberii 40 90 Setaria viridis 80 90 Datura stramonium 100 95 Sorghum halepense 20 ⁸⁰ Chenopodium album 100 90 species Ipomoea 100 90 Cyperus rotundus 90 0 Amaranthus retroflexusu 100 100 Sida spinosa 95 5 Ambrosia artemisiifólia 100 90 Sorghum vulgare 100 80 Brachiaria platyphylla 100 - Polygonum pensilvanicum 100 100 Glycine max 100 60 Helianthus annuus 100 90 Abutilon theoprasti 100 95 Panicum miliacenum 100 90 Eriochloa villosa 90 80 Setaria lutescens 70 90

141 TABLE C COMPOUND Dose 17 g / ha 2 8 postemergence Echinocloa crus-galli 95 90 Convolvulus arvensis 90 10 Solanum ptycanthum dunal 100 95 Cassia obtusifolia - 5 Xanthium strumarium 100 85 Zea mays 5 0 Gossypium hirsutum 100 40 species Digitaria 85 70 Panicum dichotomiflorum 90 90 Setaria faberii 30 90 Setaria viridis 50 90 Datura stramonium 100 95 Sorghum halepense 10 30 Chenopodium album 100 90 species Ipomoea 100 85 Cyperus rotundus 70 0 Amaranthus retroflexusu 90 100 Sida spinosa 90 0 Ambrosia artemisiifólia 100 90 Sorghum vulgare 80 5 Brachiaria platyphylla 90 - Polygonum pensilvanicum 100 100 Glycine max 100 40 Helianthus annuus 100 70 Abutilon theoprasti 100 95 Panicum miliacenum 100 90 Eriochloa villosa 80 50 Setaria lutescens 50 60

142

TABLE C COMPOUND Dose 8 g / ha 2 8 postemergence Echinocloa crus-galli 95 90 Convolvulus arvensis 90 0 Solanum ptycanthum dunal 100 85 Cassia obtusifolia - 0 Xanthium strumarium 100 70 Zea mays 0 0 Gossypium hirsutum 90 25 species Digitaria 80 10 Panicum dichotómiílorum 50 50 Setaria faberii 5 40 Setaria viridis 5 30 Datura stramonium 100 90 Sorghum halepense 0 0 Chenopodium album 100 85 species Ipomoea 100 40 Cyperus rotundus 5 0 Amaranthus retroflexusu 80 80 Sida spinosa 70 0 Ambrosia artemisiifólia 100 80 Sorghum vulgare 10 0 Brachiaria platyphylla 80 - Polygonum pensilvanicum 100 80 Glycine max 100 30 Helianthus annuus 90 - Abutilon theoprasti 100 90 Panicum miliacenum 80 90 Eriochloa villosa 30 5 Setaria lutescens 10 20

143

TABLE C COMPOUND 4 g / ha 2 8 postemergence Echinocloa crus-galli 80 80 Convolvulus arvensis 80 0 Solanum ptycanthum dunal 100 80 Cassia obtusifolia - 0 Xanthium strumarium 100 50 Zea mays 0 0 Gossypium hirsutum 90 20 species Digitaria 40 5 Panicum dichotomiflorum 5 50 Setaria faberii 0 30 Setaria viridis 0 20 Datura stramonium 100 90 Sorghum halepense 0 0 Chenopodium album 90 80 species Ipomoea 100 10 Cyperus rotundus 5 0 Amaranthus retroflexusu 40 5 Sida spinosa 65 0 Ambrosia artemisiifólia 90 5 Sorghum vulgare 0 0 Brachiaria platyphylla 50 - Polygonum pensilvanicum 90 70 Glycine max 100 10 Helianthus annuus 90 30 Abutilon theoprasti 100 90 Panicum miliacenum 70 50 Eriochloa villosa 30 5 Setaria lutescens 0 0

144

TABLE C COMPOUND

Dose 2 g / ha 8

POSTEľlERGENTNÁ

Echinocloa crus-galli 5

Convolvulus arvensis 0

Solanum ptycanthum dunal

Cassia obtusifolia 0

Xanthium strumarium 40

Zea mays

Gossypium hirsutum 10 species Digitaria 0

Panicum dichotomiflorum 0

Setaria faberii 0

Setaria viridis

Datura stramonium 90

Sorghum halepense

Chenopodium album 5 species Ipomoea 0

Cyperus rotundus 0

Amaranthus retroflexus 0

Sida spinosa

Ambrosia artemisiifolia 5

Sorghum vulgare 1

Brachiaria platyphylla

Polygonum pensilvanicum 20

Glycine max 5

Helianthus annuus

Abutilon theoprasti

Panicum miliacenum 5

Eriochloa villosa 0

Setaria lutescens

145

TEST D

The compounds evaluated in this assay were formulated in a non-phytotoxic solvent mixture that includes a surfactant and applied to the soil surface before seedlings appeared (preemergence application) and the plants were grown for various periods of time prior to treatment. ). For the pre-emergence test, clayey soil was used, yet! however, for the post-emergence test, a mixture of clayey soil and a greenhouse potting mixture was used at a ratio of E50 = 40. The test compounds were applied in the pre-emergence test approximately one day after sowing the seeds.

The withdrawal of these crops and weeds was controlled to provide plants of a suitable size for the post-emergence test. All species were grown using normal greenhouse practices. Said crop and weed species include Solanum americanuin, Sida rhombifolia, Echinochloa crus-galli, Xanthium strumarium, Chenopodium album, Ambrosia artemisiifiloa, Zea mays, Gossypium hirsutum, Solanum ptycanthum, Panicum dicotomium, Convolvumumumum, Convolvumumum, Desolvus, Ipomoea hederacea; Sorghum halepense; Polygonum persicaria; Digitaria sanguinalis; Cyperus rotundus; Amaranthus retroflexus; Glycine max;

Treated plants and untreated control plants were kept in the greenhouse for approximately 14-21 days after application of the test compound. A scale from U to 100 was used to evaluate the plant response, summarized in Table D, where 0 is no effect and 100 is a complete control. A dash (-) in the response column indicates that no result was obtained.

146

TABLE D COMPOUND

Dose 140 g / ha 8

postemergence

Sida rhombifolia 35

Echinochloa crus-galli

Xanthium strumarium

Ambrosia artemisiifiloa

Zea mays

Gossypium hirsutum

Solanum ptycanthum 100

Panicum dichotomiflorum 100

Convolvulus arvensis 80

Desmodium purpureum 100

Starla faberii 100

Bidens pilosa, 70

J

Ipomoea hederacea

Sorghum halepense

Polygonum persicaria

Chenopodiumalbum 100

Digitaria sanguinalis

Cyperus rotundus 70

Amaranthus retroflexus

Glycine max 90

Brachiaria decumbens

Abutilon theophrasti

Euphorbia heterophylla

147

TABLE D COMPOUND The rate is 70 g / ha 2 8 postemergence Sida rhombifolia 90 40 Echinochloa crus-galli 95 100 Xanthium strumarium 100 100 Ambrosia artemisiifiloa 100 100 Zea mays 10 10 Gossypium hirsutum 100 100 Solanum ptycanthum 100 100 Panicum dichotomiflorum 95 100 Convolvulus arvensis 90 65 Desmodium purpureum 100 100 Staria faberii 85 100 Bidens pilosa 75 90 Ipomoea hederacea 100 95 Sorghum halepense 50 80 Polygonum persicaria 100 100 Chenopodiumalbum 100 100 Digitaria sanguinalis 95 95 Cyperus rotundus 75 75 Amaranthus retroflexus 100 100 Glycine max 100 100 Brachiaria decumbens 85 100 Abutilon theophrasti 100 100 Euphorbia heterophylla 100 70

148

TABLE D COMPOUND The rate is 70 g / ha 2 8 PREEI4ERGENTNÁ Sida rhombifolia 95 15 Echinochloa crus-galli 70 40 Xanthium strumarium 95 10 Ambrosia artemisiifiloa 95 65 Zea mays 0 0 Gossypium hirsutum 25 15 Panicum dichotomiflorum - 100 Convolvulus arvensis 80 - Desmodium purpureum - - Staria faberii 10 80 Bidens pilosa 10 25 Ipomoea hederacea 0 15 Sorghum halepense 0 10 Polygonum persicaria - - Chenopodiumalbum 100 - Digitaria sanguinalis 100 25 Cyperus rotundus 50 45 Amaranthus retroflexus - - Glycine max - 10 Brachiaria decumbens 70 75 Abutilon theophrasti 100 100 Euphorbia heterophylla 85 30

149

TABLE D COMPOUND Dose 35 g / ha 2 3 8 POSTEľlERGENTNÁ Sida rhombifólia 85 80 35 Echinochloa crus-galli 95 90 95 Xanthium strumarium 100 100 100 Ambrosia artemisiifiloa 100 95 100 Zea mays 10 0 0 Gossypium hirsutum 100 100 100 Solanum ptycanthum 100 100 100 Panicum dichotomiflorum 85 80 100 Convolvulus arvensis 85 90 65 Desmodium purpureum 100 100 100 Staria faberii 60 65 65 Bidens pilosa 50 45 90 Ipomoea hederacea 95 95 85 Sorghum halepense 15 30 80 Polygonum persicaria 100 100 95 Chenopodiumalbum 100 100 100 Digitaria sanguinalis 90 .85 95 Cyperus rotundus 50 40 65 Amaranthus retroflexus 100 95 100 Glycine max 100 95 100 Brachiaria decumbens 80 75 75 Abutilon theophrasti 100 100 100 Euphorbia heterophylla 100 95 45

150

TABLE D COMPOUND Dose 35 g / ha 2 3 8 Pre-emergence Sida rhombifolia 95 10 10 Echinochloa crus-galli 30 20 10 Xanthium strumarium 40 25 0 Ambrosía artemisiifiloa 95 75 50 Zea mays 0 0 0 Gossypium hirsutum - 0 10 Panicum dichotomiflorum - 15 40 Convolvulus arvensis - 0 0 Desmodium purpureum - - - Staria faberii 10 0 20 Bidens pilosa 0 25 25 Ipomoea hederacea 0 20 10 Sorghum halepense 0 0 0 Polygonum persicaria - 95 30 Chenopodiumalbum 100 - - Digitaria sanguinalis 100 35 35 Cyperus rotundus 35 - 25 Amaranthus retroflexus - 100 65 Glycine max - - 0 Brachiaria decumbens 45 15 35 Abutilon theophrasti 100 80 85 Euphorbia heterophylla 75 25 55

15: .1.

TABLE D COMPOUND Dose 17 g / ha 2 3 8 POSTEľlERGENTNÁ Sida rhombifolia 80 70 25 Echinochloa crus-galli 90 60 85 Xanthium strumarium 100 100 100 Ambrosia artemisiifiloa 100 80 95 Zea mays 0 0 0 Gossypium hirsutum 100 95 85 Solanum ptycanthum 95 95 100 Panicum dichotomiflorum 70 - 95 Convolvulus arvensis 70 85 50 Desmodium purpureum 100 85 100 Staria faberii 35 30 95 Bidens pilosa 30 25 75 Ipomoea hederacea 95 90 80 Sorghum halepense 0 10 15 Polygonum persicaria 85 100 90 Ch en opodi umalbum 100 95 95 Digitaria sanguinalis 80 - 80 Cyperus rotundus 20 25 10 Amaranthus retroflexus 75 90 95 Glycine max 100 95 75 Brachiaria decumbens 65 60 70 Abutilon theophrasti 100 100 100 Euphorbia heterophylla 100 - 25

152

TABLE D COMPOUND Dose 17 g / ha 2 3 8 Pre-emergence Sida rhombifólia 50 0 0 Echinochloa crus-galli 25 0 0 Xanthium strumarium 10 0 0 Ambrosia artemisiifiloa 85 25 25 Zea mays 0 0 0 Gossypium hirsutum 10 0 0 Panicum dichotomiflorum 20 0 25 Convolvulus arvensis 25 0 0 Desmodium purpureum - - - Staria faberii 0 0 10 Bidens pilosa 0 0 25 Ipomoea hederacea - 0 - Sorghum halepense 0 0 0 Polygonum persicaria - 80 - Chenopodiumalbum 100 - - Digitaria sanguinalis 70 10 0 Cyperus rotundus 25 - 0 Amaranthus retroflexus - 100 - Glycine max - 0 0 Brachiaria decumbens 20 0 10 Abutilon theophrasti 100 75 65 Euphorbia heterophylla 15 85 15

TABLE D

COMPOUND

Dose 8 g / ha 2 3 8 postemergence Sida rhombifólia 65 40 15 Echinochloa crus-galli 85 45 75 Xanthium strumarium 100 90 95 Ambrosia artemisiifiloa 100 70 85 Zea mays 0 0 0 Gossypium hirsutum 95 90 '70 Solanum ptycanthum 90 50 75 Panicum dichotomiflorum 55 25 80 Convolvulus arvensis 50 60 40 Desmodium purpureum 100 - 95 Staria faberii 15 15 55 Bidens pilosa 25 20 65 Ipomoea hederacea 90 70 65 Sorghum halepense 0 0 ' 10 Polygonum persicaria 75 95 45 Chenopodiumalbum 100 95 95 Digitaria sanguinalis 70 60 55 Cyperus rotundus 10 10 10 Amaranthus retroflexus 65 80 85 Glycine max 100 90 65 Brachiaria decumbens 35 35 40 Abutilon theophrasti 100 95 95 Euphorbia heterophylla 95 80 20

154

TABLE D COMPOUND Dose 8 g / ha Pre-emergence 2 3 8 Sida rhombifólia 10 0 0 Echinochloa crus-galli 0 0 0 Xanthium strumarium 0 0 0 Ambrosia artemisiifiloa 10 0 0 Zea mays 0 0 0 Gossypium hirsutum 0 0 0 Panicum dichotomiflorum - 0th 10 Convolvulus arvensis - 0 - Desmodium purpureum - 0 25 Staria faberii 0 0 0 Bidens pilosa 0 0 0 Ipomoea hederacea 0 0 0 Sorghum halepense 0 0 0 Polygonum persicaria - - 0 Chenopodiumalbum 75 95 0 Digitaria sanguinalis 10 10 0 Cyperus rotundus 0 0 0 Amaranthus retroflexus - • 90 - Glycine max - 0 0 Brachiaria decumbens 0 0 0 Abutilon theophrasti 35 60 15 Euphorbia heterophylla 0 0 0

TABLE D COMPOUND 4 g / ha 2 3 8 POSTEľlERGENTNÁ Sida rhombifólia 60 35 10 Echinochloa crus-galli 70 20 45 Xanthium strumarium 95 85 85 Ambrosia artemisiifiloa 95 60 85 Zea mays 0 0 0 Gossypium hirsutum 90 85 15 Solanum ptycanthum 85 45 70 Panicum dichotomiflorum 45 10 80 Convolvulus arvensis 35 45 35 Desmodium purpureum 100 25 100 Staria faberii 15 10 15 Bidens pilosa 20 0 30 Ipomoea hederacea 90 50 55 Sorghum halepense 0 0 0 Polygonum persicaria 50 45 25 Chenopodiumalbum 95 90 75 Digitaria sanguinalis 55 35 30 Cyperus rotundus 0 0 0 Amaranthus retroflexus 35 50 80 Glycine max 95 85 60 Brachiaria decumbens 20 10 15 Abutilon theophrasti 100 90 75 Euphorbia heterophylla 85 45 15

156

TABLE D COMPOUND 4 g / ha 2 3 8 Pre-emergence Sida rhombifólia - 0 0 Echinochloa crus-galli 0 0 0 Xanthium strumarium 0 0 0 Ambrosia artemisiifiloa 0 0 0 Zea mays 0 0 0 Gossypium hirsutum - 0 - Panicum dichotomiflorum 0 0 0 Convolvulus arvensis - 0 - Desmodium purpureum . - - - Staria faberii 0 0 0 Bidens pilosa 0 0 0 Ipomoea hederacea - - - Sorghum halepense 0 0 0 Polygonum persicaria - - 0 ChenopodiurnaIbum 50 - 0 Digitaria sanguinalis 0 0 0 Cyperus rotundus 0 - 0 Amaranthus retroflexus - 0 - Glycine max - 0 0 Brachiaria decumbens 0 0 0 Abutilon theophrasti 15 20 0 Euphorbia heterophylla 0 0 0

157

TABLE D COMPOUND Dose 2 g / ha 2 3 8 postemergence Sida rhombifolia 20 25 0 Echinochloa crus-galli 25 15 15 Xanthium strumarium 90 45 45 Ambrosia artemisiifiloa 85 55 25 Zea mays 0 0 0 Gossypium hirsutum 80 40 10 Solanum ptycanthum 70 35 60 Panicum dichotomiflorum 20 0 0 Convolvulus arvensis 25 40 25 Desmodium purpureum 95 20 10 Staria faberii 10 0 0 Bidens pilosa 10 0 0 Ipomoea hederacea 65 15 0 Sorghum halepense 0 0 0 Polygonum persicaria 30 30 15 Chenopodiumalbum 95 70 20 Digitaria sanguinalis 30 15 10 Cyperus rotundus 0 0 0 Amaranthus retroflexus 15 40 70 Glycine max 80 65 25 Brachiaria decumbens 15 0 0 Abutilon theophrasti 100 35 25 Euphorbia heterophylla 55 25 10

158

TABLE D COMPOUND Dose 2 g / ha 2 3 8 PREENERGENTNÁ Sida rhombifólia - 0 0 Echinochloa crus-galli 0 0 0 Xanthium strumarium 0 0 0 Ambrosia artemisii filoa 0 0 0 Zea mays 0 0 0 Gossypium hirsutum 0 0 0 Panicum dichotomiflorum - 0 0 Convolvulus arvensis - 0 - Desmodium purpureum - - Staria faberii 0 0 0 Bidens pilosa 0 0 0 Ipomoea hederacea 0 0 - Sorghum halepense 0 - 0 Polygonum persicaria - 0 0 Chenopodiumalbum 10 85 0 Digitaria sanguinalis 0 0 0 Cyperus rotundus 0 - 0 Amaranthus retroflexus - - - Glycine max 15 - 0 Brachiaria decumbens 0 0 0 Abutilon theophrasti 10 0 0 Euphorbia heterophylla 0 0 0

159

TEST E

Plastic clay soil, prepared soil pots were partially: filled with alluvium which was then saturated with water. Seeds, tubers or plant parts selected from the group consisting of Echinochloa crus-qalli, Het & ranthera limosa, Echinochloa colonum, Echinochloa oryzicola, Ammania species, Cyperus iria, Cyperus diflormis, Leptochloa fasiculaadia seed in seed of seed of two seeds leaves. Planting and irrigation of these types of crops and weeds were planned to provide plants of a suitable size for the test. In order to reach the two-leaf stage, the water level was increased to 3 cm above the soil surface and maintained at this level for treatment, throughout the test. Chemicals formulated in a non-phytotoxic solvent blend that includes a surfactant and are applied by pipette directly to the flood water or via a hydraulic spray system with a belt conveyor for plant leaves.

Treated plants and untreated control plants were left in the greenhouse for approximately 14-21 days after application of the test compound. A scale from 0 to 100 was used to evaluate the plant response, which is summarized in Table E, in which 0 means no effect and 100 means complete control. A dash C-) in the response column indicates that no result was obtained.

•

160

TABLE E COMPOUND

Dose 64 g / ha 8

Echinochloa crus-galli

Heteranthera limosa

Echinochloa colonum 70

Echinochloa oryzicola 0

Ammania species

Cyperus iria 100

Cyperus diflormis 100

Leptochloa fasicularis 100 Directly sown Oryza sativa (Stage 2 leaves) 70 transported Oryza sativa (Stage 2 leaves) 60

TABLE E COMPOUND

Dose 32 g / ha 8

Echinochloa crus-galli

Heteranthera limosa

Echinochloa colonum 80

Echinochloa oryzicola 0

Ammania species 60

Cyperus iria 100

Cyperus diflormis 100

Leptochloa fasicularis 95 Directly sown Oryza sativa (Stage 2 leaves) 45 transported Oryza sativa (Stage 2 leaves) 35

161

TABLE E

Dose 16 g / ha

Echinochloa crus-galli Heteranthera limosa Echinochloa colonum Echinochloa oryzicola Ammania species Cyperus iria Cyperus diflormis Leptochloa fasicularis directly sown Oryza sativa transported Oryza sativa

COMPOUND ⁴⁵

100

100 (stage 2 sheets) 35 (stage 2 sheets) 30

TABLE E

Dose 8 g / ha

Echinochloa crus-galli Heteranthera limosa Echinochloa colonum Echinochloa oryzicola Ammania species Cyperus iria Cyperus diflormis Leptochloa fasicularis directly sown Oryza sativa transported Oryza sativa

COMPOUND

65 80 (Stage 2 Letters) 40 (Stage 2 Letters) 20

162

TABLE E COMPOUND Dose 4 g / ha 8

Echinochloa crus-galli O Heteranthera limosa 55 Echinochloa colonum O Echinochloa oryzicola 10 Aminania species O Cyperus iria 90 Cyperus diflormis 45 Leptochloa fasicularis 50 Directly sown Oryza sativa C Stage 2 leaves 20 Transported 10 Oryza sativa 10

TEST F

Seeds, tubers or plant parts of Brachiaria plantaginae, Cynodort dactylon, Brachiaria plantyphylla, Portulaca oleracea, Ambrosia elatior, Paspalum dilatatum, Eleusine indica, Panicum maxima, Rottboellia exaltata, Rotaria hypogeosa, Cyanususundusis, Cyanususundisisus, Cysticususundusis, Trichachne insularis and Brachiaria decumbens were planted in greenhouse pots or areas containing greenhouse seed medium. Plant species were grown in separate pots or individual compartments. Test chemicals were formulated in a non-phytotoxic solvent composition containing a surfactant and applied to the plants preemergence and postemergence. Preemergence applications were performed on the day the seeds were sown or plant parts were planted. Post-emergence treatment was performed at the time when the plants had grown to two to four leaf stage (three to twenty)

163 centimeters).

Treated plants and untreated control plants were kept in the greenhouse for approximately 13-21 days after application of the test compound. To assess the plant response, which is summarized in Table F, a scale from f) to 100 was used, in which 0 means no effect and 100 means complete control. A dash <-) in the response column indicates that no result was obtained.

TABLE F COMPOUND

Dose 125 g / ha 2

postemergence

Brachiaria plantaginea 100

Cynodon dactylon 95

Brachiaria plantyphylla

Portulaca oleracea

Ambrosia elatior

Gossypium hirsutum 100

Paspalum dilatatum

Eleusine indica

Panicum maximum 40

Rottboellia exaltata

Sorghum halepense

Digitaria sanguinalis 90

Arachis hypogaea

Ipomoea lacunosa 100

Cyperus rotundus 65

Cenchrus echinatus

Trichachne insularis 80

Brachiaria decumbens

164

TABLE F

COMPOUND

Dose 125 q / ha 2

Pre-emergence

Brachiaria plantaginea 35

Cynodon dactylon 75

Brachiaria plantyphylla 20

Portulaca oleracea

Ambrosia elatior

Gossypium hirsutum

Paspalum dilatatum 25

Rottboellia exaltata

Sorghum halepense

Digitaria sanguinalis

Ara ch i s hypogaea 25

Ipomoea lacunosa 90

Cyperus rotundus 0

Cenchrus echinatus

100

Brachiaria decumbens

165

TABLE F

COMPOUND

Dose 64 g / ha 2 POSTEMERGENT

Brachiaria plantaginea 80 Cynodon dactylon 90 Brachiaria plantyphylla 98 Portulaca oleracea 98 Ambrosia elatior 85 Gossypium hirsutum 100 Paspalum dilatatum 75 Eleusine indica 75 Panicum maximum 20 Trichachne insularis 80 Brachiaria decumbens 70

166

TABLE F COMPOUND

Dose 64 g / ha 2

Pre-emergence

Brachiaria plantaginea

Cynodon dactylon 65

Brachiaria plahtyphylla

Portulaca oleracea 65

Ambrosia elatior

Gossypium hirsutum

Paspalum dilatatum 0

Rottboellia exaltata

Sorghum halepense

Digitaria sanguinalis

Ara ch i s hypogaea 0

Ipomoea lacunosa 1

Cyperus rotundus 0

Cenchrus echinatus

100

Brachiaria decumbens 0

TEST G

The compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture that included a surfactant and applied to the soil surface before seedlings appeared (pre-emergence application) and the plants were allowed to grow to two to four leaves Cpostemergent prior to further treatment. application). Clay-clay soil was used for the pre-emergence test, while a mixture of clay-soil and greenhouse mixture was used for the post-emergence

167

60:40. Test compounds were administered in the case of the pre-emergence test, approximately one day after sowing the seeds.

The withdrawal of these crop and weed species was controlled to provide plants of a suitable size for the post-emergence test. All species were grown using normal greenhouse practices. Said crop and weed species include Poa artnua, Solanum nigra, Alopecurus myosuroides, Stellaria media, Laminum aplexicaule, Bromus tectorum, Viola arvensis. gallium

aparine, Setaria viridis, Ae il ilops cylindrica, Kochia Chenopodium album, Phalaris rninor, Brassica napus, retroflexus, Lolium multiflorum, tlatricaria inodora, persica venti, Hordeum vulgare variety Triticum aestivum variety Talent.

scoparia.

amaranths

Veronica aestivum arvensis, Irgi a

Avena fatua was treated in two growth stages. The first stage C1) was a two to three listml stage. The second stage (C 2) was the stage at which the plant had approximately four leaves or the early stages of the plant expelling offshoots. Treated plants and untreated control plants were kept in the greenhouse for approximately 21 to 28 days after application of the test compound, after which time they were compared with the control plants and evaluated visually. To evaluate the plant response, which is summarized in Table G, a scale from 0 to 100 was used in which 0 means no effect and 100 means complete control. A dash C-) in the response column indicates that no result was obtained.

168

TABLE 6 COMPOUND Dose 31 g / ha 4 8 9 POSTEľlERGENTNÁ Poa annua 0 - 5 Alopecurus myosuroides 0 10 5 Solanum nigra 100 90 10 Stellaria media 0 - 0 Laminum amplexicaule 90 85 10 Bromus tectorum 10 0 5 Viola arvensis 0 80 - Gallium aparine 65 40 35 Setaria viridis 10 100 0 Aegilops cylindrica 5 0 5 Kochia scoparia 35 - 0 Chenopodium album 100 45 40 Phalaris minor 0 0 5 Brassica napus 30 - 15 Amaranths retroflexus 85 50 65 Lolium multiflorum 5 0 0 Matricaria inodora 80 45 70 Veronica persica 30 80 0 Hordeum vulgare 'Klages' 10 0 0 Beta vulgaris discourages 'US' 100 - 100 Helianthus annuus varieties' Russian Gianť 75 - 5 Triticum aestivum 'ERA' 15 0 0 Triticum aestivum 'Talent' 15 0 0 Poolygonum convolvulus 0 10 0 Sinapis arvensis 100 100 70 Avena fatua (2) - 0 - Avena fatua (1) 5 5 0 Apera spica-venti 0 0 5 Hordeum vulgare 'Irgi' 5 0 0

169

TABLE G

Dose 31 g / ha

Pre-emergence

Poa annua

Alopecurus myosuroides

Solanum nigra

Stellaria media

Laminum amplexicaule

Bromus tectorum

Gallium aparine

Setaria viridis

Aegilops cylindrica

Kochia scoparia

Chenopodium album

Phalaris minor

Amaranths retroflexus

Lolium multiflorum

Matricaria inodora

Veronica persica

Hordeum vulgare varietas 'Klages' Triticum aestivum varietas 'ERA' Triticum aestivum varieties 'Talent' Poolygonum convolvulus Sinapis arvensis

Avena fatua (2)

Apera spica-venti

Hordeum vulgare 'Irgľ

COMPOUND

170

TABLE G COMPOUND

Dose 16 g / ha postemergence 4 8 9 Poa annua 0 - 0 Alopecurus myosuroides 0 10 0 Solanum nigra 30 80 0 Stellaria media 0 100 0 Laminum amplexicaule 35 90 5 Bromus tectorum 0 0 0 Viola arvensis 0 80 0 Gallium aparine 10 65 0 Setaria viridis 5 85 0 Aegilops cylindrica 0 0 0 Kochia scoparia 0 - 0 Chenopodium album 30 50 - Phalaris minor 0 0 0 Brassica napus 0 - 0 Amaranths retroflexus 60 55 - Lolium multiflorum 5th 0 0 Matricaria inodora 70 50 40 Veronica persica 15 80 0 Hordeum vulgare 'Klages' 0 0 0 Beta vulgaris variety 'USľ 35 - 70 Helianthus annuus 'Russian Gianť' 0 - 0 Triticum aestivum 'ERA' 0 0 0 Triticum aestivum 'Talent' 0 0 0 Poolygonum convolvulus 0 10 0 Sinapis arvensis 50 100 85 Avena fatua (2) - 0 - Avena fatua (1) 0 0 0 Apera spica-venti 0 0 0 Hordeum vulgare 'Irgľ 0 0 0

171

TABLE G

Dose 16 g / ha

F'REEľlERGENTNÁ

Poa annua

Alopecurus myosuroides

Solanum nigra

Stellaria media

Laminum amplexicaule

Bromus tectorum

Gallium aparine

Setaria viridis

Aegilops cylindrica

Kochia scoparia

Chenopodium album

Phalaris minor

Amaranths retroflexus

Lolium multiflorum

Matricaria inodora

Veronica persica

Hordeum vulgare varietas 'Klages' Triticum aestivum varietas 'ERA' Triticum aestivum varieties 'Talent' Poolygonum convolvulus Sinapis arvensis

Avena fatua (2)

Apera spica-venti

Hordeum vulgare 'Irgľ

COMPOUND o

80th

172

TABLE G

COMPOUND

Dose 8 g / ha 4 POSTEMERGENT

Poa annua 0 Alopecurus myosuroides 0 Solanum nigra 10 Stellaria media 0 Laminum amplexicaule 0 Bromus tectorum 0 Viola arvensis 0 Gallium aparine 0 Setaria viridis 0 Aegilops cylindrica 0 Kochia scoparia 0 Chenopodium album 0 Phalaris minor 0 Brassica napus 5 Amaranth

Lolium multiflorum 0 Matricaria inodora

Veronica persica 0 Hordeum vulgare variety 'Klages' 0 Beta vulgaris variety 'US' 25 Helianthus annuus variety 'Russian Gian' 0 Triticum aestivum variety 'ERA' 0 Triticum aestivum variety 'Talent' 0 Poolygonum convolvulus 0 Sinapis arvensis 30 Avena fatua (1)

Avena fatua (2) 0 Apera spica-venti 0 Hordeum vulgare

0 '

173

TABLE G

Dose 8 g / ha

PREEľlERGENTNÁ

Poa annua

Alopecurus myosuroides

Solanum nigra

Stellaria media

Laminum amplexicaule

Bromus tectorum

Gallium aparine

Setaria viridis

Aegilops cylindrica

Kochia scoparia

Chenopodium album

Phalaris minor

Amaranths retroflexus

Lolium multiflorum

Matricaria inodora

Veronica persica

Hordeum vulgare varietas 'Klages' Triticum aestivum varietas 'ERA' Triticum aestivum varieties 'Talent' Poolygonum convolvulus Sinapis arvensis

Avena fatua (2)

Apera spica-venti

Hordeum vulgare 'Irgi'

COMPOUND

8 o

174

TABLE G

COMPOUND

4 g / ha 4

postemergence

Poa annua 1

Alopecurus myosuroides

Solanum nigra

Stellaria media 0

Laminum amplexicaule 0

Bromus tectorum

Viola arvensis 0

Gallium aparine 0

Setaria viridis

Aegilops cylindrica 1

Kochia scoparia 1

Chenopodium album 0

Phalaris minor 0

Brassica napus 0

Amaranths retroflexus 30

Lolium multiflorum

He has three tsars and an inodora 20

Veronica persica

Hordeum vulgare 'Klages' 0

Beta vulgaris variety 'US 15

Helianthus annuus varietas' Russian Gianť 0

Triticum aestivum variety 'ERA' 0

Triticum aestivum variety 'Talent' 0

Poolygonum convolvulus 0

Sinapis arvensis 30

Avena fatua (2)

Avena fatua (1) 0

Apera spica-venti

Hordeum vulgare 'Irgi' 0

0 o

about

175

TABLE G

4 g / ha

Pre-emergence

Poa annua

Alopecurus myosuroides

Solanum nigra

Stellaria media

Laminum amplexicaule

Bromus tectorum

Gallium aparine

Setaria viridis

Aegilops cylindrica

Kochia scoparia

Chenopodium album

Phalaris minor

Amaranths retroflexus

Lolium multiflorum

Matricaria inodora

Veronica persica

Hordeum vulgare variety 'Klages' Triticum aestivum variety 'ERA' Triticum aestivum variety 'Talent' Poolygonum convolvulus Sinapis arvensis

Avena fatua (2)

Apera spica-venti

Hordeum vulgare 'Irgi'

COMPOUND ¹⁰ o

o o

o o

o o

o o

o o

7Ψ

176

Claims (8)

PATENT A compound having the appropriate salts of the general formula I and agriculturally in which 1 to 6 carbon atoms, 6 carbon atoms or carbon atoms, or R ¹ R ¹ and R ²⁵ are independently alkoxy carbon, haloalkoxy of 2 to alkylthio of 1 to 6 haloalkylthio of 2 to 6 R ² together are -X-C ^J · CH), --- X ² -, - _{<CH2) S-X} ~ _t -X ³ -CH 2 CCH) vX ³ -CH2CK ₂ - or -CCH _{S W} -, wherein each group may be optionally substituted with at least one member selected from the group consisting of 1 to 6 halogen atoms, 1 to 6 methyl groups, and one alkoxy group with 1 to 3 carbon atoms; or R ¹ and R ² together may be -O-NCC 1 -C 3 alkyl) -CHR ¹² -CHS- or -ON = CHR ¹² -CH 2 -, wherein each group may be optionally substituted with at least one member selected from the group consisting of 1 to 2 halogen atoms and 1 to 2 methyl groups; or R ^{@ 1} and R ^{@ 2} together with the carbon atom, can 177 which are bound to form CdO) or CC = S); X ^{: L} and X '^;'are independently O, S or C 1 -C 6 alkyl); X ⁵ is an oxygen or sulfur atom; each IT ⁷³ is independently hydrogen or methyl; R ' ⁴ ' and F ^' are independently hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio C 1 -C 6 haloalkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl 6 carbon atoms, cyano, nitro group; a halogen atom; or R is OR ^{1: 1} , alkyl 11 haloalkylthio with 1 1 to 6 carbon atoms, up to 6 carbon atoms, (C 1 -C 6) alkylsulphinyl, (C 1 -C 6) halogen, C (1-6C) alkylatoms, balloon (C 1 -C 6) alkylsulfinyl, (C 1 -C 6) sulfonyl, (C 1 -C 6), thiocyanate or halo; each R ⁷ is independently C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -C 3 alkylthio or halogen; or where two R ⁷ bound to the same carbon atom, then the pair of substituents R ⁷ 'may together form a -OCH O-, -OCHaCHs-CHaO-, _and -SCH CH _R or S -SCHsCHsCH ^ S, and each R it may be optionally substituted with one to four methyl groups; 178 R ° is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, formyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl (C-C alky) alkylaininocarbonyl, (C až-C dial) dialkylaminocarbonyl, (C až-C alkyl) alkylsulfonyl or halogen, (C až-C alkyl) alkylsulfonyl or R '' means benzoyl or phenylsulphonyl an onyl group which may be optionally substituted by a alkyl group having 1 to 3 carbon atoms, a halogen atom, a cyano group or a nitro group; R ⁵ * represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms or an alkynyl group having 3 to 6 carbon atoms; ⁵ 'represents a phenyl or benzyl group which may be optionally substituted by an alkyl group having 1 to 3 carbon atoms, a halogen atom, a cyano group or a nitro group; R ( ¹⁰⁾ is hydrogen, (C1-C6) alkyl, (C1-C6) haloalkyl, halogen, cyano or nitro; R ¹¹ represents a hydrogen atom, a C 1 -C 6 alkyl group, a C 1 -C 6 haloalkyl group, a C 2 -C 6 alkoxyalkyl group, a formyl group, a C 2 -C 6 alkylcarbonyl group, a C 2 -C 6 alkoxycarbonyl group C 1 -C 6 alkyl, C 2 -C 6 alkylaininocarbonyl, C 3 -C 7 dialkylaminocarbonyl, C 1 -C 6 alkylsulfonyl or C 1 -C 6 haloalkylsulfonyl; or R ¹¹ represents a benzoyl or phenylsulfonyl group, 179 which may be optionally substituted by C 1 -C 3 alkyl, halogen, cyano or n 11; R ¹² represents an alkyl group with; 1 to 3 carbon atoms; or R ' ² represents a phenyl group which may be optionally substituted by an alkyl group having 1 to 3 carbon atoms, a halogen atom, a cyano group or a nitro group; X means (SCO) an oxygen atom; NR ¹³ ; R ¹³ means hydrogen, alkyl group having 1 to 3 atoms atoms, alkenyl; 3 to 4 carbon atoms, an alkynyl group having from 3 to 4 carbon u h 1 k a, f o r m y 1 o u group. a1k y1k arbonyl group with 2 to 3 and th a m i u h h i k, C 2 -C 3 alkoxycarbonyl or C 1 -C 2 alkylsulfonyl; Y represents an oxygen atom; a sulfur atom; NH; NCCx-C alkyl); or CH ® optionally substituted with R ⁷ if q is not 0; represents a direct bond; an oxygen atom; SC Cl); NH; NC C _x - C ₃ of alkyl); or CH-. optionally substituted with R ⁷ if g is not O; provided that when Y is O, S, NH and NCC _t-C3 alkyl), and Z is a direct bond or a C I to ₂ substituent optionally substituted or R '''; k and m are independently: 0 or 2; d p o k 1 a d e: that the sum of k and m is 0, 1 or 2; n and p are g is 0, r is 2, independently: 0, 1 or 2; 1, 2, 3 or 4; 3 or 4; 180 denotes 2, 3, 4 or 5; denotes 1, 2, 3 or 4; is 2 or 3; u represents 2, 3, 4, 5 or 6; x is 1 or 2; and z is 0, 1 or 2; pr ± assuming that 0 is 0-1 and R ¹ and R ³² are i (i) when X is S (O) _r is not 1 s 1 and 1 is 1-ethoxy and 1 is 1 to Ei having 1 to E 1 carbon atoms, C 1 -C 6 alkyl, C 1 -C 6 alkylthio or C 2 -C 6 haloalkylthio or together: with the carbon atom to which they are attached form C (= O), then n is 1 or 2; and (ii) when X is an oxygen atom or MR ¹³ and R ¹ and R ³² are 1 to 6 1 to G is 1 to 1 and 1 is 1 to 1 alkoxy to 11 (oxy) alkylthio of 1 to E atoms of alkylthio of 2 to 6 carbon atoms, carbon, carbon or halogen atoms or together with the carbon atom to which bind to form C (= O), then O is 0-2. A compound according to claim 1 wherein uc; and each R ⁷ 'is independently C 1 -C 3 alkyl or halogen; 181 X is S (O) _r ,; Y and Z are independently Cl-I-. optionally substituted with R ^x ; l <is 0; . and x is 1. 3. The compound according to claim 2, characterized ut characterized in that uc: ar r 2 · alpha _{and marks} AMEN independently: C 1 -C 6 alkoxy, haloalkoxy of 2 to EC carbon atoms, alkylthio of 1 to 6 carbon atoms, or haloalkylthio having 2 to 8 carbon atoms; or R 1 and R ² together form -XMCH 3 -R ² optionally substituted by at least one member selected from 1 to ES halogens and 1 to ES methyl groups; or R ¹ and R ^a together represent the carbon atom to which they are attached, 0 (= 0): X ¹ and X ² are both oxygen or sulfur; is 1 or 2; and r is 2 or 3. 4. A compound according to claim 3, wherein: R ⁺ and ^R are independently: H, alkyl radical having 1 to 3 carbon atoms or a hydrogen atom; R ⁵ 'represents an alkyl group having 1 to 3 carbon atoms; R.? represents a hydrogen atom, an alkyl group 1 to E> atoms 182 carbon or a (C 3 -C 6) alkenyl group; R @ ⁵ denotes hydrogen; is hydrogen, formyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 7 dialkylaminocarbonyl, alkylsulfonyl or haloalkyl sulfones 1 to 6 carbon atoms; or R ¹¹ represents a benzoyl or phenylsulfonyl group which may be optionally substituted by a C 1 -C 3 alkyl group, a halogen atom, a cyano group or a benzo group; and n is 2. 5. A compound according to claim 4, wherein: R ¹ and R ² are methoxy; or R ¹ and R ² together form - X ¹ - CCH - X ² -; and R ¹ and R ² form at least 1 carbon atom to which they are attached (CC = O); X ¹ and X ² are oxygen; ^R are each independently H, methyl or halogen; group R ⁶ is (R ¹¹ ; R ¹³ represents a hydrogen atom or an alkylsulfonyl group having 1 to 6 carbon atoms; or R 8 represents a benzoyl or phenylsulfonyl group, each of which may be optionally substituted with an alkyl group of 1 to 3 183 carbon atoms, halogen atoms, cyano or nitro; R ^{1: 1} represents a hydrogen atom or an alkylsulfonyl group having 1 to 2 carbon atoms; or R ¹¹ is benzoyl or phenylsulfonyl, each of which may be optionally substituted with C 1 -C 3 alkyl, halogen, cyano or nitro; m is 1; and r is 2. 6. The compound of claim 5, wherein R ⁵ is methyl or halogen and is attached to a ring position adjacent to feriylového -S-O) _r, - en to clamp. 7. A compound according to claim 3, selected from the group consisting of: 2-C (2,3-dihydrospiro [4- (7-1-benzathiopyrrole-4,2'-Cl, 33 dioxolanl-6-yl) carbonyl] -1,3-cyclohexanedione S, S-dioxide; (2,3-dihydrospiro (4 H) -1-benzothiopyran-4,2 '- (1,3' dioxolanl-6-yl) (1-ethyl-5-hydroxy-1 H -pyrazol-4-yl) metharion S S-dioxide; 2-CC2, 3-dihydro-5,8-dimethylspiroC4 / 7-1-benzothiopyran-4,2'-Cl, 33d dioxoanil 3-6-yl) carbones 13 -1,3-cyclohexyl ndi ó n S, 5'-dioxide; C 2, 3-dihydro-5,8-dimethylspiro C 4 H -Z-1-benzothiopyran-4,2'-Cl, 33-dioxolane; 6-yl) (1-ethyl-5-hydroxy-3 H -pyrazol-4-yl) methanone S, S-dioxide; 6-CCl-ethyl-5-hydroxy-1H-pyrazol-4-yl) carbonyl-2,3-dihydro-5,8184 - d im ethyl-4 / 7-1 - b e n o t i o p y r - n - 4 - o n -1, 1 - cl o x i d s 2-CC2, 3-dihydro-5,8-dimethylspiro (4H-1-benzothiopyran-4,2'-Cl, 33-dioxolanl-6-yl) carbonyl-1,3-cyclohexanediol; and C 2,3-dihydro-5,8-d: MethylspiroC4 / 7-1-benzothiopyran-4,2'-Cl, 33-dioxolanl-6-yl) (1-ethyl-5-hydroxy-1H-pyrazol-4-yl) ) methanone. 8. A herbicidal composition. characterized in that it contains a herbicidally effective amount of a compound according to claim 3 and at least one additive selected from a surfactant, a diluent and a quencher. e d i d 1 a. A method of controlling the growth of undesirable, in which the environment is brought into contact from the third day of the day. (a) an indication of vegetation: or a herbicidally effective amount thereof